JP2021101007A - Block polyisocyanate composition, hydrophilic polyisocyanate composition, resin composition, resin film and laminate - Google Patents

Abstract

To provide a block polyisocyanate composition which has good storage stability when being used as a resin composition, and has good low temperature curability when being used as a resin film.SOLUTION: A block polyisocyanate composition contains block polyisocyanate derived from polyisocyanate and a blocking agent, and an anionic dispersant. The blocking agent contains (A) a compound represented by the following formula (I), where R11 represents an alkoxy group or the like, R12 represents a hydrogen atom or the like, and R13 and R14 represent an alkyl group or the like, or (B) a compound having a heterocycle containing one or more nitrogen. The anionic dispersant has surface tension at 25°C of an aqueous solution composed of 0.1 mass% of the anionic dispersant based on the total mass of the aqueous solution and water, which is measured by a Wilhelmy method, of 32 mN/m or more and 51 mN/m or less. When the blocking agent is a compound having a heterocycle having one or more of the (B) nitrogen, the blocking agent further contains carboxylate.SELECTED DRAWING: None

Description

The present invention relates to a blocked polyisocyanate composition, a hydrophilic polyisocyanate composition, a resin composition, a resin film and a laminate.

Conventionally, polyurethane resin paints have very excellent wear resistance, chemical resistance and stain resistance. In particular, polyurethane resin coating materials using polyisocyanates obtained from aliphatic diisocyanates or alicyclic diisocyanates have further excellent weather resistance, and the demand for them tends to increase. However, since polyurethane resin paints are generally two-component, their use is extremely inconvenient. That is, a normal polyurethane resin paint is composed of two components, a polyol and a polyisocyanate, and it is necessary to store the polyol and the polyisocyanate separately and mix them at the time of coating. Further, once the two are mixed, the paint gels in a short time and cannot be used. Since the polyurethane resin coating material has such a problem, it is extremely difficult to use it for automatic coating in the field of line coating such as automobile coating or weak electric coating. Moreover, since isocyanate easily reacts with water, it cannot be used in water-based paints such as electrodeposition paints. Further, when a paint containing isocyanate is used, it is necessary to sufficiently clean the coating machine and the coating tank at the end of the work, so that the work efficiency is significantly lowered.

In order to improve the above-mentioned problems, it has been conventionally proposed to use a blocked polyisocyanate in which all active isocyanate groups are blocked with a blocking agent. This blocked polyisocyanate does not react with polyols at room temperature. However, by heating, the blocking agent is dissociated, the active isocyanate group is regenerated, and the reaction with the polyol causes a cross-linking reaction, so that the above-mentioned problems can be improved. Therefore, many blocking agents have been studied, and for example, phenol, methyl ethyl ketooxime and the like can be mentioned as typical blocking agents.

However, when a blocked polyisocyanate using these blocking agents is used, a high baking temperature of 140 ° C. or higher is generally required. The need for baking at a high temperature is not only disadvantageous in terms of energy, but also requires heat resistance of the base material, which is a factor that limits its use.

On the other hand, as a low-temperature baking type block polyisocyanate, research has been conducted on block polyisocyanates using active methylene compounds such as acetoacetic ester and malonic acid diester. For example, Patent Documents 1 and 2 propose block polyisocyanate compositions that cure at 90 ° C.

Japanese Unexamined Patent Publication No. 2002-322238 Japanese Unexamined Patent Publication No. 2006-335954

However, in recent years, from the viewpoint of protecting the global environment and adaptation to plastics having low heat resistance, there is a strong demand for a block polyisocyanate composition that cures at a temperature lower than 90 ° C. Under such circumstances, it has good dispersibility when mixed with respect to aqueous polyols having hydroxyl groups (aqueous dispersion polyols), does not gel or excessively thicken during storage, and has curability at 80 ° C. or lower. The good ones are still unknown.

The present invention has been made in view of the above circumstances, and has good storage stability when made into a resin composition and good curability at a low temperature of about 80 ° C. when made into a resin film. The present invention provides a block polyisocyanate composition, and a resin composition, a resin film, and a laminate using the block polyisocyanate composition.
Further, a hydrophilic polyisocyanate composition having good water dispersibility and excellent hardness when formed into a resin film, and a blocked polyisocyanate composition, a resin composition and the like using the hydrophilic polyisocyanate composition. A resin film is provided.

The present invention includes the following aspects.
(1) Blocked polyisocyanates derived from polyisocyanates and one or more types of blocking agents, and
Anionic dispersant and
A blocked polyisocyanate composition containing
The blocking agent is (A) a compound represented by the following general formula (I),
Or (B) a compound having a heterocycle containing one or more nitrogens,
Including
The anionic dispersant has a surface tension of 0.1% by mass based on the total mass of the aqueous solution measured by the Wilhelmi method at 25 ° C. of the aqueous solution consisting of the anionic dispersant and water of 32 mN /. M or more and 51 mN / m or less,
A blocked polyisocyanate composition, wherein the blocking agent further comprises a carboxylic acid salt when the blocking agent contains a compound having a heterocycle containing one or more of the nitrogen (B).

(In the general formula (I), R ¹¹ is a hydroxy group; an alkyl group which may contain one or more substituents selected from the group consisting of a hydroxy group and an amino group; and a group consisting of a hydroxy group and an alkyl group. Amino group which may contain one or more substituents selected; aryl group which may contain one or more substituents selected from the group consisting of hydroxy group and amino group; or which consists of hydroxy group and amino group It is an alkoxy group that may contain one or more substituents selected from the group. However, the amino group may be formed by connecting two of the substituents to each other to form a ring.
R ¹² , R ¹³ and R ¹⁴ each independently consist of a hydrogen atom; an alkyl group which may contain one or more substituents selected from the group consisting of a hydroxy group and an amino group; or a hydroxy group and an amino group. It is an aryl group that may contain one or more substituents selected from the group. The amino group may be formed by connecting the two substituents to each other to form a ring. However, ^{two or more of R 12} , R ¹³ and R ¹⁴ are not hydrogen atoms. )
(2) Blocked polyisocyanates derived from polyisocyanates and one or more types of blocking agents, and
Anionic dispersant and
A blocked polyisocyanate composition containing
The blocking agent contains a compound represented by the following general formula (I).
The anionic dispersant has a surface tension at 25 ° C. of 32 mN /% of the aqueous solution composed of the anionic dispersant and water, which is 0.1% by mass based on the total mass of the aqueous solution, as measured by the Wilhelmi method. A blocked polyisocyanate composition having a mass of m or more and 51 mN / m or less.

(In the general formula (I), R ¹¹ is a hydroxy group; an alkyl group which may contain one or more substituents selected from the group consisting of a hydroxy group and an amino group; and a group consisting of a hydroxy group and an alkyl group. Amino group which may contain one or more substituents selected; aryl group which may contain one or more substituents selected from the group consisting of hydroxy group and amino group; or which consists of hydroxy group and amino group It is an alkoxy group that may contain one or more substituents selected from the group. However, the amino group may be formed by connecting two of the substituents to each other to form a ring.
R ¹² , R ¹³ and R ¹⁴ each independently consist of a hydrogen atom; an alkyl group which may contain one or more substituents selected from the group consisting of a hydroxy group and an amino group; or a hydroxy group and an amino group. It is an aryl group that may contain one or more substituents selected from the group. The amino group may be formed by connecting the two substituents to each other to form a ring. However, ^{two or more of R 12} , R ¹³ and R ¹⁴ are not hydrogen atoms. )
(3) The blocked polyisocyanate composition according to (1) or (2) above, wherein a part or all of the blocked polyisocyanate has a structural unit derived from a hydrophilic compound.
(4) The block according to (3) above, wherein the structural unit derived from the hydrophilic compound contains at least one hydrophilic group selected from the group consisting of a nonionic hydrophilic group and an anionic hydrophilic group. Polyisocyanate composition.
(5) In the blocking agent, the general formula (I) ^{, wherein R 11} is an alkoxy group, R ¹² is a hydrogen group or an alkyl group, and R ¹³ and R ^{14 are alkyl groups.} The blocked polyisocyanate composition according to any one of (1) to (4) above, which comprises one or more of the compounds represented by.
(6) Any one of (1) to (5) above, wherein the content of the anionic dispersant is 0.01 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the blocked polyisocyanate. The blocked polyisocyanate composition according to.
(7) The blocked polyisocyanate composition according to any one of (1) to (6) above, wherein the blocked polyisocyanate contains a blocked isocyanurate trimer.
(8) The blocked polyisocyanate composition according to any one of (1) to (7) above, wherein the polyisocyanate has an average number of isocyanate functional groups of 2.0 or more.
(9) Any one of (1) to (8) above, wherein the polyisocyanate is a polyisocyanate derived from one or more kinds of diisocyanates selected from the group consisting of an aliphatic diisocyanate and an alicyclic diisocyanate. The blocked polyisocyanate composition according to.
(10) The blocked polyisocyanate composition according to (1) above, wherein the blocking agent contains (B) a compound having a heterocycle containing one or more nitrogen.
(11) The blocked polyisocyanate composition according to (10) above, wherein the content of the counter cation of the carboxylate is 0.1% by mass or more and 20% by mass or less with respect to the total mass of the blocked polyisocyanate. Stuff.
(12) The blocked polyisocyanate composition according to (10) or (11) above, wherein the carboxylic acid salt is a carboxylic acid metal salt or a quaternary ammonium cation carboxylate.
(13) The blocked polyisocyanate composition according to (12) above, wherein the carboxylic acid salt is a carboxylic acid metal salt.
(14) The block polyisocyanate composition according to (13) above, wherein the metal species of the carboxylic acid metal salt is a monovalent metal.
(15) The block according to any one of (10) to (14) above, wherein the compound having a heterocycle containing one or more nitrogen is a compound having a heterocycle containing two or more nitrogen. Polyisocyanate composition.
(16) The blocked polyisocyanate composition according to (15) above, wherein the blocking agent is a compound having a heterocycle containing three or more nitrogens.
(17) A resin composition containing the block polyisocyanate composition according to any one of (1) to (16) above and a multivalent hydroxy compound.
(18) The resin composition according to (17) above, wherein the glass transition temperature Tg of the multivalent hydroxy compound is 0 ° C. or higher and 100 ° C. or lower.
(19) the weight average molecular weight of polyhydroxy compound is 2.0 × 10 ⁵ or less 5.0 × 10 ³ or more, the (17) or the resin composition according to (18).
(20) The resin composition according to any one of (17) to (19) above, wherein the hydroxyl value of the multivalent hydroxy compound is 30 mgKOH / g or more and 250 mgKOH / g or less.
(21) The item according to any one of (17) to (20) above, wherein the content of the blocked polyisocyanate is 5 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the polyvalent hydroxy compound. Resin composition.
(22) A resin film obtained by curing the resin composition according to any one of (17) to (21) above.
(23) The gel fraction when a resin film having a thickness of 40 μm obtained by heating the resin composition at 80 ° C. for 30 minutes and curing it is stored at 23 ° C. for 1 week and then immersed in acetone at 23 ° C. for 24 hours. The resin film according to (22) above, which is 80% by mass or more.
(24) A resin film having a film thickness of 40 μm, a width of 10 mm and a length of 40 mm formed by heating and curing the resin composition at 80 ° C. for 30 minutes is set so that the distance between chucks is 20 mm, and the speed is 20 mm / min. The resin film according to (22) or (23) above, wherein the tensile strength in the tensile test carried out in (2) or (23) is 5 MPa or more.
(25) A laminate containing two or more layers of the resin film according to any one of (22) to (24) having different compositions.
A laminate having a thickness of 1 μm or more and 50 μm or less per layer of the laminate.
(26) A hydrophilic polyisocyanate composition derived from a hydrophilic compound and an alicyclic polyisocyanate having an isocyanurate group.
A hydrophilic polyisocyanate composition in which the ratio of isocyanate groups modified with the hydrophilic compound to the total molar amount of isocyanate groups of the alicyclic polyisocyanate is 2 mol% or more and 15 mol% or less.
(27) The hydrophilic polyisocyanate composition according to (26) above, which comprises a polyisocyanate having an isocyanurate group, wherein the alicyclic polyisocyanate is derived from isophorone diisocyanate.
(28) The hydrophilic polyisocyanate composition according to (26) or (27) above, wherein the alicyclic polyisocyanate has an average number of functional groups of 2.5 or more and 6.0 or less.
(29) The hydrophilic polyisocyanate composition according to any one of (26) to (28), wherein the hydrophilic polyisocyanate composition has a weight average molecular weight of 900 or more and 20000 or less.
(30) The hydrophilic polyisocyanate composition according to any one of (26) to (29) above, wherein the hydrophilic compound is a nonionic compound or an anionic compound.
(31) A blocked polyisocyanate composition, wherein at least a part of the isocyanate groups in the hydrophilic polyisocyanate composition according to any one of (26) to (30) is sealed with a blocking agent.
(32) The block according to (31) above, wherein the blocking agent is at least one compound selected from the group consisting of an active methylene compound, an oxime compound, an amine compound, a pyrazole compound, and a triazole compound. Polyisocyanate composition.
(33) A resin composition containing the hydrophilic polyisocyanate composition according to any one of (26) to (30) above and a polyol.
(34) A resin composition containing the blocked polyisocyanate composition according to (31) or (32) above and a polyol.
(35) A resin film obtained by curing the resin composition according to (33) or (34).

According to the block polyisocyanate composition of the above aspect, the block poly which has good storage stability when it is made into a resin composition and has good curability at a low temperature of about 80 ° C. when it is made into a resin film. An isocyanate composition can be provided. The resin composition of the above aspect has good storage stability. The resin film of the above aspect has good curability at a low temperature of about 80 ° C. The laminate of the above aspect contains two or more layers of the resin film having different compositions, and the resin film has good curability at a low temperature of about 80 ° C.
According to the hydrophilic polyisocyanate composition of the above aspect, it is possible to provide a hydrophilic polyisocyanate composition having good water dispersibility and excellent hardness when formed into a resin film. The blocked polyisocyanate composition obtained by sealing the hydrophilic polyisocyanate composition with a blocking agent has good water dispersibility and excellent hardness when formed into a resin film. The polyisocyanate composition or the resin composition containing the block polyisocyanate composition is excellent in hardness when formed into a resin film.

Hereinafter, embodiments for carrying out the present invention (hereinafter, referred to as “embodiments”) will be described in detail. The present invention is not limited to the following embodiments.

As used herein, the term "polyol" means a compound having two or more hydroxy groups (-OH).
As used herein, the term "polyisocyanate" means a reaction product in which a plurality of monomer compounds having one or more isocyanate groups (-NCO) are bonded.

≪Block polyisocyanate composition≫
The blocked polyisocyanate composition of the first embodiment of the present invention comprises a polyisocyanate, a blocked polyisocyanate derived from one or more blocking agents, and an anionic dispersant.

The blocking agent is (A) a compound represented by the following general formula (I) (hereinafter, may be referred to as “compound (I)”), or (B) a compound having a heterocycle containing one or more nitrogen. including.

(In the general formula (I),
R ¹¹ may contain one or more substituents selected from the group consisting of hydroxy groups; hydroxy groups and amino groups. Alkyl groups; one or more substituents selected from the group consisting of hydroxy groups and alkyl groups. An amino group which may contain an amino group; an aryl group which may contain one or more substituents selected from the group consisting of a hydroxy group and an amino group; or one or more kinds selected from the group consisting of a hydroxy group and an amino group. It is an alkoxy group that may contain a substituent. However, the amino group may be formed by connecting the two substituents to each other to form a ring.
The R ^12, R ¹³ and R ¹⁴ are each independently a hydrogen atom; the group consisting or hydroxy group and an amino group; hydroxy group and an alkyl group that may contain one or more substituents selected from the group consisting of amino group It is an aryl group that may contain one or more substituents that are more selected. The amino group may be formed by connecting the two substituents to each other to form a ring. However, ^{two or more of R 12} , R ¹³ and R ¹⁴ are not hydrogen atoms. )

Further, in the anionic dispersant, the surface tension of the aqueous solution composed of the anionic dispersant and water, which is 0.1% by mass based on the total mass of the aqueous solution, measured by the Wilhelmi method at 25 ° C. is 32 mN. It is / m or more and 51 mN / m or less, preferably 34 mN / m or more and 50 mN / m or less, more preferably 36 mN / m or more and 48 mN / m or less, and further preferably 37 mN / m or more and 47 mN / m or less. When the surface tension is within the above range, the storage stability of the resin composition can be kept good.

Conventionally, a blocked polyisocyanate composition using a malonic acid ester having a secondary alkyl group or a tertiary alkyl group (for example, diisopropyl malate, di-tert-butyl malonate, etc.) as a blocking agent has a low temperature of about 80 ° C. However, it has high reactivity with hydroxyl groups of polyvalent hydroxy compounds such as polyols to be reacted, and when stored as a resin composition containing a main agent and a curing agent, a significant increase in viscosity and gelation are likely to occur. There was a problem. In particular, the above problem is remarkable in a mixed solution of a blocked polyisocyanate composition using a malonic acid ester having a tertiary alkyl group as a blocking agent (for example, malonic acid-di-tert-butyl, etc.) and an aqueous polyol. It appeared in, and the improvement was desired.

On the other hand, the blocked polyisocyanate composition of the present embodiment can improve the above-mentioned problems by containing an anionic dispersant having a surface tension in the above range, and the blocked polyisocyanate composition and the polyvalent hydroxy It is possible to effectively suppress an increase in viscosity and gelation during storage of a mixed solution with a compound, and to exhibit good storage stability.

As the method for measuring the surface tension, for example, the following method can be used for the measurement. First, the anionic dispersant is diluted with water to prepare an aqueous solution containing 0.1% by mass of the anionic dispersant and water with respect to the total mass of the aqueous solution. Then, using the aqueous solution, the surface tension at 25 ° C. is measured by the Wilhelmi method (also called the plate method or the vertical plate method). As a specific measurement method, when the plate, which is a stylus, comes into contact with the surface of the aqueous solution, the aqueous solution gets wet with respect to the plate. At this time, surface tension acts along the periphery of the plate, and a force that tries to draw the plate into the aqueous solution acts. The pulling force F (force acting on the plate, measuring force) can be read, and the surface tension r can be measured by the following formula. In the formula, L is the perimeter (m) of the plate, and θ is the contact angle between the plate and the aqueous solution.

r = F / (L × cosθ)

The surface tension can also be measured using a commercially available measuring device, for example, a static surface tension measuring system (manufactured by DKSH Japan, model number: TD 1C or TD 3).

Hereinafter, each component contained in the block polyisocyanate composition of the present embodiment will be described in detail.

<Block polyisocyanate>
Blocked polyisocyanate is a reaction product of polyisocyanate and a blocking agent. That is, in the blocked polyisocyanate, at least a part of the isocyanate groups in the polyisocyanate are blocked with a blocking agent.

The blocked polyisocyanate can have one or more functional groups selected from the group consisting of an allophanate group, a uretdione group, an iminooxadiazinedione group, an isocyanurate group, a urethane group and a biuret group. Above all, it is preferable to contain an isocyanurate group because it has excellent weather resistance.

The blocked polyisocyanate preferably contains a blocked isocyanurate trimer. The term "isocyanurate trimer" as used herein means a polyisocyanate derived from three molecules of an isocyanate monomer and having an isocyanurate group. Further, the “blocked isocyanurate trimer” means that at least a part (preferably all) of the isocyanate groups in the isocyanurate trimer is blocked with a blocking agent. By containing the blocked isocyanurate trimer, the heat resistance when made into a resin film tends to be more excellent.

[Polyisocyanate]
The polyisocyanate used for producing a blocked polyisocyanate is a reaction product obtained by reacting a plurality of monomer compounds having one or more isocyanate groups (-NCO) (hereinafter, may be referred to as "isocyanate monomer"). Is.
The isocyanate monomer preferably has 4 or more and 30 or less carbon atoms. Specific examples of the isocyanate monomer include the following. These isocyanate monomers may be used alone or in combination of two or more.
(1) Aromatic diisocyanates such as diphenylmethane-4,4'-diisocyanate (MDI), 1,5-naphthalenediocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate, and m-tetramethylxylene diisocyanate (TMXDI).
(2) 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (hereinafter, may be referred to as "HDI"), 2,2,4-trimethyl-1,6-diisocyanatohexane, 2, Aliphatic diisocyanates such as 4,4-trimethyl-1,6-hexamethylene diisocyanate, 2-methylpentane-1,5-diisocyanate (MPDI), and lysine diisocyanate (hereinafter, may be referred to as "LDI").
(3) Fats such as isophorone diisocyanate (hereinafter sometimes referred to as "IPDI"), 1,3-bis (diisocyanate methyl) cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, diisocyanate norbornane, di (isocyanet methyl) norbornane, etc. Cyclic diisocyanate.
(4) 4-Isocyanate Methyl-1,8-octamethylene diisocyanate (hereinafter, may be referred to as "NTI"), 1,3,6-hexamethylene triisocyanate (hereinafter, may be referred to as "HTI"). , Bis (2-isocyanatoethyl) 2-isocyanatoglutarate (hereinafter, may be referred to as "GTI"), lysocyanate triisocyanate (hereinafter, may be referred to as "LTI") and the like.

Among them, since the weather resistance is excellent, the isocyanate monomer is preferably one or more kinds of diisocyanates selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates. Further, the isocyanate monomer is more preferably HDI or IPDI from the viewpoint of easy industrial availability. Further, the isocyanate monomer is more preferably HDI from the viewpoint of lowering the viscosity of the blocked polyisocyanate component.

(Manufacturing method of polyisocyanate)
The method for producing polyisocyanate will be described in detail below.
Polyisocyanates are, for example, allophanate formation reaction to form an allophanate group, uretdione formation reaction to form a uretdione group, iminooxadiazine diionization reaction to form an iminooxadiazinedione group, isocyanurate formation to form an isocyanurate group. The reaction, the urethanization reaction to form a urethane group, and the biuretization reaction to form a biuret group are produced at once in the presence of an excess of isocyanate monomer, and the unreacted isocyanate monomer is removed after the reaction is completed. be able to. That is, the polyisocyanate obtained by the above reaction is a group in which a plurality of the above-mentioned isocyanate monomers are bonded and is composed of an allophanate group, a uretdione group, an iminooxadiazinedione group, an isocyanurate group, a urethane group and a biuret group. It is a reactant having one or more kinds selected from the above.
Further, the above reactions may be carried out separately, and the obtained polyisocyanates may be mixed in a specific ratio.
From the viewpoint of simplicity of production, it is preferable to carry out the above reaction at once to obtain polyisocyanate, and from the viewpoint of freely adjusting the molar ratio of each functional group, it is preferable to produce them separately and then mix them.

For example, as a catalyst for deriving a polyisocyanate containing an isocyanurate group from an isocyanate monomer, a commonly used isocyanurate-forming reaction catalyst can be mentioned.

The isocyanurate-forming reaction catalyst is not particularly limited, but is generally preferably one having basicity. Specific examples of the isocyanurate-forming reaction catalyst include those shown below.
1) Hydrooxides of tetraalkylammoniums such as tetramethylammonium, tetraethylammonium, and tetrabutylammonium, and acetates, propionates, octylates, capricates, myristates, and benzoates of the tetraalkylammonates. Organic weak salts such as.
2) Hydroxide of aryltrialkylammonium such as benzyltrimethylammonium and trimethylphenylammonium, and acetate, propionate, octylate, capricate, myristate, benzoate and the like of the aryltrialkylammonium. Organic ammonium salt.
3) Hydroxide of hydroxyalkylammonium such as trimethylhydroxyethylammonium, trimethylhydroxypropylammonium, triethylhydroxyethylammonium, triethylhydroxypropylammonium, and acetate, propionate, octylate, capric acid of the hydroxyalkylammonium. Organic weak acid salts such as salts, myristates, and benzoates.
4) Metal salts of alkylcarboxylic acids such as acetic acid, propionic acid, caproic acid, octyl acid, caproic acid and myristic acid such as tin, zinc and lead.
5) Metalal alcoholates such as sodium and potassium.
6) Aminosilyl group-containing compound such as hexamethylene disilazane.
7) Mannich bases.
8) A mixture of tertiary amines and an epoxy compound.
9) Phosphorus compounds such as tributylphosphine.

Among them, from the viewpoint of less likely to generate unnecessary by-products, the isocyanurate-forming reaction catalyst is preferably a quaternary ammonium hydrooxide or a quaternary ammonium organic weak acid salt, and a tetraalkylammonium hydrooxide, More preferably, it is an organic weakened salt of tetraalkylammonium, a hydroxide of aryltrialkylammonium, or an organic weakened salt of aryltrialkylammonium.

The upper limit of the amount of the isocyanurate-forming reaction catalyst used is preferably 1000 mass ppm, more preferably 500 mass ppm, and 100 mass ppm with respect to the mass of the charged isocyanate monomer. Is even more preferable.
On the other hand, the lower limit of the amount of the isocyanurate-forming reaction catalyst used is not particularly limited, but may be, for example, 10 mass ppm.

The isocyanurate-forming reaction temperature is preferably 50 ° C. or higher and 120 ° C. or lower, and more preferably 55 ° C. or higher and 90 ° C. or lower. When the isocyanurate-forming reaction temperature is not more than the above upper limit value, coloring of polyisocyanate and the like tend to be suppressed more effectively.

When the desired conversion rate (the ratio of the mass of the polyisocyanate produced by the isocyanurate-forming reaction to the mass of the charged isocyanate monomer) is reached, the isocyanurate-forming reaction is carried out with an acidic compound (for example, phosphoric acid, acidic phosphoric acid). It is stopped by the addition of (ester, etc.).
In order to obtain polyisocyanate, it is necessary to stop the progress of the reaction at an early stage. However, since the initial reaction rate of the isocyanurate-forming reaction is very fast, it is difficult to stop the progress of the reaction at the initial stage, and the reaction conditions, particularly the amount and method of addition of the catalyst must be carefully selected. is there. For example, a method of dividing and adding the catalyst at regular time intervals is recommended as a suitable method.
Therefore, the conversion rate of the isocyanurate-forming reaction for obtaining a polyisocyanate is preferably 10% or more and 60% or less, more preferably 15% or more and 55% or less, and 20% or more and 50% or less. Is even more preferable.
When the conversion rate of the isocyanurate-forming reaction is not more than the above upper limit value, the blocked polyisocyanate component can have a lower viscosity. Further, when the conversion rate of the isocyanurate-forming reaction is at least the above lower limit value, the reaction stop operation can be performed more easily.

Further, when inducing a polyisocyanate containing an isocyanurate group, an alcohol having a valence of 1 or more and 6 or less can be used in addition to the above-mentioned isocyanate monomer.
Examples of the monohydric or higher and hexavalent or lower alcohols that can be used include non-polymerizable alcohols and polymerizable alcohols. The term "non-polymerizable alcohol" as used herein means an alcohol having no polymerizable group. On the other hand, the "polymerizable alcohol" means an alcohol obtained by polymerizing a monomer having a polymerizable group and a hydroxyl group.
Examples of the non-polymerizable alcohol include polyhydric alcohols such as monoalcohols, diols, triols and tetraols.
Examples of monoalcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, n-pentanol, n-hexanol, n-octanol, n-nonanol, and 2-ethylbutanol. , 2,2-Dimethylhexanol, 2-ethylhexanol, cyclohexanol, methylcyclohexanol, ethylcyclohexanol and the like.
Examples of diols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, and 1, 3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol, 2-methyl-2,3-butanediol, 1, 6-Hexanediol, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, 2-ethyl-hexanediol, 1,2-octanediol, 1,2-decanediol, 2,2,4-trimethylpentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propane Examples include diol.
Examples of triols include glycerin, trimethylolpropane and the like.
Examples of tetraols include pentaerythritol and the like.

The polymerizable alcohol is not particularly limited, and examples thereof include polyester polyols, polyether polyols, acrylic polyols, and polyolefin polyols.

The polyester polyols are not particularly limited, and examples thereof include products obtained by a condensation reaction between a dibasic acid alone or a mixture and a polyhydric alcohol alone or a mixture.
The dibasic acid is not particularly limited, but is at least one selected from the group consisting of carboxylic acids such as succinic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride, phthalic acid anhydride, isophthalic acid, and terephthalic acid. Species of dibasic acid.
The polyhydric alcohol is not particularly limited, and examples thereof include at least one polyhydric alcohol selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, trimethylolpropane, and glycerin.
Examples of polyester polyols include polycaprolactones obtained by ring-opening polymerization of ε-caprolactone using the above-mentioned polyhydric alcohol.

The polyether polyols are not particularly limited, but for example, an alkali metal hydroxide or a strongly basic catalyst is used to add an alkylene oxide alone or a mixture to a polyhydric alcohol alone or a mixture. Examples thereof include polyether polyols obtained by reacting a polyamine compound with an alkylene oxide, and so-called polymer polyols obtained by polymerizing acrylamide or the like using the above-mentioned polyethers as a medium.
Examples of the alkali metal include lithium, sodium, potassium and the like.
Examples of the strong basic catalyst include alcoholates and alkylamines.
Examples of the polyhydric alcohol include those similar to those exemplified in the above polyester polyols.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide and the like.
Examples of the polyamine compound include ethylenediamines.

The acrylic polyols are not particularly limited, but for example, an ethylenically unsaturated bond-containing monomer having a hydroxyl group alone or a mixture thereof and another ethylenically unsaturated bond-containing monomer copolymerizable therewith are used alone. Alternatively, a copolymer of a mixture may be used.
The ethylenically unsaturated bond-containing monomer having a hydroxyl group is not particularly limited, and is, for example, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyhydroxymethacrylate. Butyl and the like can be mentioned.
The other ethylenically unsaturated bond-containing monomer copolymerizable with the ethylenically unsaturated bond-containing monomer having a hydroxyl group is not particularly limited, and is, for example, an acrylic acid ester, a methacrylic acid ester, or an unsaturated carboxylic acid. , Unsaturated amides, vinyl-based monomers, and vinyl-based monomers having a hydrolyzable silyl group.
Examples of the acrylic acid ester include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, -n-butyl acrylate, isobutyl acrylate, -n-hexyl acrylate, cyclohexyl acrylate, and -2 acrylate. -Ethylhexyl, lauryl acrylate, benzyl acrylate, phenyl acrylate and the like can be mentioned.
Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, -n-hexyl methacrylate, cyclohexyl methacrylate, and -2 methacrylic acid. -Ethylhexyl, lauryl methacrylate, benzyl methacrylate, phenyl methacrylate and the like can be mentioned.
Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, itaconic acid and the like.
Examples of unsaturated amides include acrylamide, methacrylamide, N, N-methylenebisacrylamide, diacetoneacrylamide, diacetonemethacrylamide, maleic acid amide, and maleimide.
Examples of the vinyl-based monomer include glycidyl methacrylate, styrene, vinyltoluene, vinyl acetate, acrylonitrile, dibutyl fumarate and the like.
Examples of the vinyl-based monomer having a hydrolyzable silyl group include vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, and the like.

Examples of polyolefin polyols include hydroxyl-terminated polybutadiene and hydrogenated products thereof.

The allophanate reaction, the uretdione reaction, the iminooxadiazine dione reaction, the isocyanurate-forming reaction, the urethanization reaction, and the biuret-forming reaction may be carried out sequentially, or some of them may be carried out in parallel. ..
The unreacted isocyanate monomer can be removed from the reaction solution after completion of the reaction by thin film distillation, extraction or the like to obtain polyisocyanate.

Further, for the purpose of suppressing coloration during storage, for example, an antioxidant or an ultraviolet absorber may be added to the obtained polyisocyanate.
Examples of the antioxidant include hindered phenols such as 2,6-di-tert-butyl-p-cresol. Examples of the ultraviolet absorber include benzotriazole, benzophenone and the like. These antioxidants and ultraviolet absorbers may be used alone or in combination of two or more. The amount of these additions is preferably 10 mass ppm or more and 500 mass ppm or less with respect to the mass of the polyisocyanate.

(Average number of isocyanate functional groups of polyisocyanate)
The average number of isocyanate functional groups of the polyisocyanate is preferably 2.0 or more in terms of enhancing the low-temperature curability when formed into a resin film, and the low-temperature curability when formed into a resin film and the polyhydric alcohol compound. From the viewpoint of compatibility with each other, 3.0 or more is more preferable, 4.6 or more and 20 or less is further preferable, and 5 or more and 10 or less is particularly preferable.
The average number of isocyanate functional groups of polyisocyanate can be measured by using the method described in Examples described later.

[Blocking agent]
The blocking agent used for producing the blocked polyisocyanate includes (A) a compound represented by the following general formula (I) (compound (I)). The blocking agent may contain the compound (I) alone or in combination of two or more.

(Compound (I))
(1) R ¹¹
In the general formula (I), R ¹¹ is selected from the group consisting of a hydroxy group; an alkyl group which may contain one or more substituents selected from the group consisting of a hydroxy group and an amino group; and a group consisting of a hydroxy group and an alkyl group. An amino group which may contain one or more substituents; an aryl group which may contain one or more substituents selected from the group consisting of a hydroxy group and an amino group; or a group consisting of a hydroxy group and an amino group. An alkoxy group that may contain one or more substituents of choice. However, the amino group may be formed by connecting the two substituents to each other to form a ring.

When R ¹¹ is an alkyl group having no substituent, the alkyl group preferably has 1 or more and 30 or less carbon atoms, more preferably 1 or more and 8 or less, and 1 or more and 6 or less. It is more preferable, and it is particularly preferable that it is 1 or more and 4 or less. Specific examples of the alkyl group having no substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a sec-butyl group, an isobutyl group, and an n-pentyl group. Isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n -Heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3- Examples thereof include ethyl pentyl group, 2,2,3-trimethylbutyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group and the like.

When R ¹¹ is an alkyl group having a substituent, the substituent is a hydroxy group or an amino group.
Examples of the alkyl group containing a hydroxy group as the substituent include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group and the like.
Examples of the alkyl group containing an amino group as the substituent include an aminomethyl group, an aminoethyl group, an aminopropyl group, an aminobutyl group and the like.
Examples of the alkyl group containing a hydroxy group and an amino group as the substituent include a hydroxyaminomethyl group, a hydroxyaminoethyl group, a hydroxyaminopropyl group and the like.

When R ¹¹ is an amino group having a substituent, the substituent is a hydroxy group or an alkyl group.
Examples of the amino group having a hydroxy group as a substituent include a hydroxyamino group (-NH-OH).
Examples of the amino group having an alkyl group as a substituent include a methylamino group, an ethylamino group, an n-butylamino group, a dimethylamino group, a diethylamino group, a dipropylamino group, a diisopropylamino group and a di-n-butylamino group. Examples thereof include a group, a di-tert-butylamino group, a di-sec-butylamino group, a diisobutylamino group, a 2,6-dimethylpiperidyl group and the like.
Examples of the amino group having a hydroxy group and an alkyl group as the substituent include a hydroxymethylene amino group, a hydroxyethylene amino group, a hydroxypropylene amino group, a hydroxybutylene amino group and the like.
Examples of the amino group in which the two substituents are linked to each other to form a ring include an ethyleneimino group, an azacyclobutyl group, a pyrrolidyl group, a piperidyl group, a 2,6-dimethylpiperidyl group and a hexamethyleneimino group. Cyclic secondary amino group of.

When R ¹¹ is an aryl group having no substituent, the aryl group preferably has 5 or more and 30 or less carbon atoms, more preferably 6 or more and 20 or less, and 6 or more and 14 or less. Is even more preferable. Specifically, the aryl group is, for example, a monocyclic aromatic hydrocarbon group, a bicyclic aromatic hydrocarbon group, a tricyclic aromatic hydrocarbon group, a tetracyclic aromatic hydrocarbon group, or a pentacyclic aromatic group. Examples thereof include an aromatic hydrocarbon group, a 6-ring aromatic hydrocarbon group, and a 7-ring aromatic hydrocarbon group.
Examples of the monocyclic aromatic hydrocarbon group include a phenyl group, a benzyl group, a tolyl group, an o-xylyl group and the like.
Examples of the bicyclic aromatic hydrocarbon group include an indanyl group, an indenyl group, a pentarenyl group, an azulenyl group, a naphthyl group, a tetrahydronaphthyl group and the like.
Examples of the tricyclic aromatic hydrocarbon group include anthrasenyl group, fluorenyl group, phenalenyl group, phenanthrenyl group and the like.
Examples of the tetracyclic aromatic hydrocarbon group include a pyrenyl group, a naphthalsenyl group, a chrysenyl group and the like.
Examples of the pentacyclic aromatic hydrocarbon group include a perylenel group, a pisenyl group, a pentasenyl group and the like.
Examples of the hexacyclic aromatic hydrocarbon group include a naphthopyrenyl group and the like.
Examples of the 7-cyclic aromatic hydrocarbon group include a coronenyl group and the like.

When R ¹¹ is an aryl group having a substituent, the substituent is a hydroxy group or an amino group.
Examples of the aryl group containing a hydroxy group as a substituent include a phenol group and the like.
Examples of the aryl group containing an amino group as a substituent include an aniline group and the like.
Examples of the aryl group containing a hydroxy group and an amino group as the substituent include an aminophenol group (hydroxyaniline group) and the like.

When R ¹¹ is an alkoxy group having no substituent, the alkoxy group preferably has 1 or more and 30 or less carbon atoms, more preferably 1 or more and 8 or less, and 1 or more and 6 or less. It is more preferable, and it is particularly preferable that it is 1 or more and 4 or less. Specifically, as the alkoxy group, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, a sec-butoxy group, an isobutoxy group, an n-pentoxy group, an isopentoxy group, Neopentoxy group, tert-pentoxy group, 1-methylbutoxy group, n-hexitoxy group, 2-methylpentoxy group, 3-methylpentoxy group, 2,2-dimethylbutoxy group, 2,3-dimethylbutoxy group, n -Heptoxy group, 2-methylhexitoxy group, 3-methylhexitoxy group, 2,2-dimethylpentoxy group, 2,3-dimethylpentoxy group, 2,4-dimethylpentoxy group, 3,3-dimethylpentoxy group, Examples thereof include 3-ethylpentoxy group, 2,2,3-trimethylbutoxy group, n-octoxy group, isooctoxy group, 2-ethylhexitoxy group, noninoxy group, decyloxy group and the like.

When R ¹¹ is an alkoxy group having a substituent, the substituent is a hydroxy group or an amino group.
Examples of the alkoxy group containing a hydroxy group as a substituent include a hydroxymethyleneoxy group, a hydroxyethyleneoxy group, a hydroxypropyleneoxy group, a hydroxybutyleneoxy group and the like.
Examples of the alkoxy group containing an amino group as a substituent include an aminomethyleneoxy group, an aminoethyleneoxy group, an aminopropyleneoxy group, an aminobutyleneoxy group and the like.
Examples of the alkoxy group containing a hydroxy group and an amino group as the substituent include a hydroxyaminomethylidineoxy group, a hydroxyaminoethylidineoxy group, a hydroxyaminoproppyridineoxy group and the like.

Among them, as R ^11, preferably it is or without alkoxy group having a substituent, an alkoxy group having no substituent and more preferably.

(2) R ¹² , R ¹³ and R ¹⁴
In general formula (I), R ¹² , R ¹³ and R ¹⁴ are each independently an alkyl group which may contain one or more substituents selected from the group consisting of a hydrogen atom; a hydroxy group and an amino group; or a hydroxy group. It is an aryl group that may contain one or more substituents selected from the group consisting of groups and amino groups. The amino group may be formed by connecting the two substituents to each other to form a ring. However, ^{two or more of R 12} , R ¹³ and R ¹⁴ are not hydrogen atoms.
Examples of the alkyl group and the aryl group include those similar to those exemplified in the ^{above “R 11”.}
Examples of the amino group in which the above two substituents are linked to each other to form a ring include a cyclic secondary amino group such as an ethyleneimino group, an azacyclobutyl group, a pyrrolidyl group and a piperidyl group.
Among them, a or without alkyl radical having R ¹² is a hydrogen atom or a substituent, and, independently R ¹³ and R ¹⁴ each is preferably or without alkyl group having a substituent, R ¹² is More preferably, it is an alkyl group having no hydrogen atom or a substituent, and R ¹³ and R ¹⁴ have no substituents independently.

^{In compound (I), R 11} is an alkoxy group, R ¹² is a hydrogen atom or an alkyl group, and R ¹³ and R are excellent because of their excellent industrial availability and curability at low temperature. ^{It is preferable that 14} is an alkyl group. The blocking agent may contain the compound (I) having the above composition alone or in combination of two or more.

Further, since the compound (I) has a tert-butyl ester structure or a tert-pentyl ester structure, it is excellent in low-temperature curability when formed into a resin film, and also has a sec-butyl ester structure or an iso-propyl ester structure. As a result, the storage stability of the resin composition tends to be excellent.

Specific preferred compounds (I) include, for example, di-tert-butyl malonic acid, di-tert-pentyl malonic acid, di-sec-butyl malonic acid, diisopropyl malonic acid, tert-butyl ethyl malonate, and malon. Examples thereof include isopropylethyl acid acid.
Of these, di-tert-butyl malonic acid, di-tert-pentyl malonic acid, di-sec-butyl malonic acid or diisopropyl malonic acid are preferable from the viewpoint of low-temperature curability when formed into a resin film, and have water dispersion stability. From the viewpoint, di-tert-butyl malonic acid or diisopropyl malonic acid is more preferable.

As the blocking agent used in the production of the blocked polyisocyanate, (B) a compound having a heterocycle containing one or more nitrogens can also be used.
The compound having a heterocycle containing at least one nitrogen (B) is preferably a compound having a heterocycle containing two or more nitrogens, and contains three or more nitrogens, from the viewpoint of low temperature curability. More preferably, it is a compound having a heterocycle.

Examples of the compound having a heterocycle containing one or more nitrogens include those shown below.
1) Aziridine-based blocking agent such as ethyleneimine;
2) Azetidine-based blocking agents such as azecyclobutane;
3) Azolidine-based blocking agents such as pyrrolidine;
4) Azole-based blocking agents such as pyrrole, 2H-pyrrole;
5) Imidazoline-based blocking agents such as 2-methylimidazoline and 2-phenylimidazolin;
6) Pyrimidine-based blocking agents such as 2-methyl-1,4,5,6-tetrahydropyrimidine;
7) Pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, imidazole, 2-methylimidazole, 4-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-ethyl-4 -Diazole-based blocking agents such as methylimidazole, 2-phenylimidazole, 4-methyl-2-phenylimidazole, benzoimidazole, 2-methylbenzoimidazole;
8) Triazole-based blocking agents such as 1,2,4-triazole, 1,2,3-triazole, 3,5-dimethyl-1,2,4-triazole;
9) Tetrazole-based blocking agent such as 1H-1,2,3,4-tetrazole.
Among these, 8) triazole-based blocking agents such as 1,2,4-triazole and 1,2,3-triazole are preferable.

(Other blocking agents)
The blocking agent used for producing the blocked polyisocyanate is, in addition to the above-mentioned compound (I) or (B) a compound having a heterocycle containing one or more nitrogens, storage stability and a resin film when prepared as a resin composition. In addition, other blocking agents may be contained as long as the low-temperature curability is not impaired.
The content of the compound having a heterocycle containing one or more of the above compounds (I) or (B) nitrogen is 5 mol% or more based on the total molar amount of all the blocking agents used in the production of the blocked polyisocyanate. It is preferably 50 mol% or more, more preferably 70 mol% or more, further preferably 80 mol% or more, and particularly preferably 90 mol% or more. Most preferably, it is 100 mol%.
When the content of the compound having a heterocycle containing one or more of the above compounds (I) or (B) nitrogen is within the above range, the low temperature curability of the resin film can be further improved.

Examples of other blocking agents include 1) alcohol-based compounds, 2) alkylphenol-based compounds, 3) phenol-based compounds, 4) active methylene-based compounds other than compound (I), 5) mercaptan-based compounds, and 6) acid amides. System compounds, 7) Acidimide-based compounds, 8) Imidazole-based compounds, 9) Urea-based compounds, 10) Oxim-based compounds, 11) Amine-based compounds, 12) Imid-based compounds, 13) Dipersulfate, 14) Pyrazole-based Compounds, 15) Triazole compounds and the like can be mentioned. More specific examples of the blocking agent include those shown below.

1) Alcohol-based compounds: Alcohols such as methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol and the like.
2) Alkylphenol compounds: Mono and dialkylphenols having an alkyl group having 4 or more carbon atoms as a substituent. Specific examples of alkylphenol compounds include n-propylphenol, iso-propylphenol, n-butylphenol, sec-butylphenol, tert-butylphenol, n-hexylphenol, 2-ethylhexylphenol, n-octylphenol, and n-nonylphenol. Monoalkylphenols such as: di-n-propylphenol, diisopropylphenol, isopropylcresol, di-n-butylphenol, di-tert-butylphenol, di-sec-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol, etc. Dialkylphenols such as di-n-nonylphenol.
3) Phenolic compounds: phenol, cresol, ethylphenol, styrenated phenol, hydroxybenzoic acid ester, etc.
4) Active methylene compounds: dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, etc.
5) Mercaptan compounds: Butyl mercaptan, dodecyl mercaptan, etc.
6) Acid amide compounds: acetanilide, acetate amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, etc.
7) Acid-imide compounds: succinimide, maleate imide, etc.
8) Imidazole compounds: imidazole, 2-methylimidazole, etc.
9) Urea compounds: urea, thiourea, ethylene urea, etc.
10) Oxime compounds: formaldehyde, acetaldoxime, acetoxime, methylethylketooxime, cyclohexanone oxime and the like.
11) Amine compounds: diphenylamine, aniline, carbazole, din-propylamine, diisopropylamine, isopropylethylamine and the like.
12) Imine compounds: ethyleneimine, polyethyleneimine, etc.
13) Sodium bisulfite compound: sodium bisulfite and the like.
14) Pyrazole compounds: pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole and the like.
15) Triazole compounds: 3,5-dimethyl-1,2,4-triazole and the like.

[Hydrophilic compound]
The blocked polyisocyanate contained in the blocked polyisocyanate composition of the present embodiment may have a structural unit in which a part or the whole thereof is derived from a hydrophilic compound.
That is, the blocked polyisocyanate contained in the blocked polyisocyanate composition of the present embodiment may be a part or all of the hydrophilic blocked polyisocyanate.

Since the hydrophilic compound reacts with one isocyanate group, it is preferable that one molecule of the hydrophilic compound has one or more active hydrogen groups for reacting with the isocyanate group of the polyisocyanate. Specific examples of the active hydrogen group include a hydroxyl group, a mercapto group, a carboxylic acid group, an amino group, and a thiol group.

Examples of the hydrophilic group include a nonionic hydrophilic group, a cationic hydrophilic group, and an anionic hydrophilic group. These hydrophilic groups may be used alone or in combination of two or more. Among them, as the hydrophilic group, a nonionic hydrophilic group is preferable from the viewpoint of easy availability and less susceptible to electrical interaction with the formulation, and from the viewpoint of suppressing a decrease in hardness of the obtained resin film, from the viewpoint of suppressing a decrease in hardness of the obtained resin film. Anionic hydrophilic groups are preferred.

(Hydrophilic compound with nonionic hydrophilic group)
Specific examples of the hydrophilic compound having a nonionic hydrophilic group include monoalcohols and compounds in which ethylene oxide is added to the hydroxyl groups of alcohols. Examples of the monoalcohol include methanol, ethanol, butanol and the like. Examples of the compound in which ethylene oxide is added to the hydroxyl group of the alcohol include ethylene glycol, diethylene glycol, polyethylene glycol, polyethylene glycol monomethyl ether and the like. These hydrophilic compounds having a nonionic hydrophilic group also have an active hydrogen group that reacts with an isocyanate group.
The number of ethylene oxides added to the compound to which ethylene oxide is added is preferably 4 or more and 30 or less, and more preferably 4 or more and 20 or less. When the number of ethylene oxides added is not less than the above lower limit, water dispersibility tends to be more effectively imparted to the blocked polyisocyanate composition, and when the number of ethylene oxides added is not more than the above upper limit. Precipitates of the blocked polyisocyanate composition tend to be less likely to occur during low temperature storage.
Among them, as the hydrophilic compound having a nonionic hydrophilic group, monoalcohol is preferable because the water dispersibility of the blocked polyisocyanate composition can be improved with a small amount of use.

The lower limit of the amount of nonionic hydrophilic groups added to the blocked polyisocyanate (hereinafter, may be referred to as "content of nonionic hydrophilic groups") is from the viewpoint of water dispersion stability of the blocked polyisocyanate composition. Therefore, 1% by mass is preferable, 2% by mass is more preferable, 3% by mass is further preferable, and 4% by mass is particularly preferable with respect to the mass of the solid content of the blocked polyisocyanate composition.
The upper limit of the content of the nonionic hydrophilic group is preferably 30% by mass, preferably 20% by mass, based on the mass of the solid content of the blocked polyisocyanate composition from the viewpoint of water resistance of the obtained resin film. More preferably, 18% by mass is further preferable, and 15% by mass is particularly preferable.
That is, the content of the nonionic hydrophilic group is preferably 1% by mass or more and 30% by mass or less, more preferably 2% by mass or more and 20% by mass or less, based on the mass of the non-volatile content of the blocked polyisocyanate composition. It is more preferably mass% or more and 18% by mass or less, and particularly preferably 4% by mass or more and 15% by mass or less.
When the content of the nonionic hydrophilic group is within the above range, the blocked polyisocyanate composition is more dispersed in water, and the water resistance of the obtained resin film tends to be improved.

(Hydrophilic compound having a cationic hydrophilic group)
Specific examples of the hydrophilic compound having a cationic hydrophilic group include a compound having both a cationic hydrophilic group and an active hydrogen group. Further, a compound having an active hydrogen group such as a glycidyl group and a compound having a cationic hydrophilic group such as sulfide and phosphine may be combined to form a hydrophilic compound. In this case, a compound having an isocyanate group and a compound having an active hydrogen group are reacted in advance to add a functional group such as a glycidyl group, and then a compound such as sulfide or phosphine is reacted. From the viewpoint of ease of production, a compound having both a cationic hydrophilic group and an active hydrogen group is preferable.

Specific examples of the compound having both a cationic hydrophilic group and an active hydrogen group include dimethylethanolamine, diethylethanolamine, diethanolamine, methyldiethanolamine and the like. Further, the tertiary amino group added using these compounds can be quaternized with, for example, dimethyl sulfate or diethyl sulfate.

The reaction of a hydrophilic compound having a cationic hydrophilic group with a polyisocyanate can be carried out in the presence of a solvent. The solvent in this case is preferably one that does not contain an active hydrogen group, and specific examples thereof include ethyl acetate, propylene glycol monomethyl ether acetate, and dipropylene glycol dimethyl ether.

The cationic hydrophilic group added to the blocked polyisocyanate is preferably neutralized with a compound having an anionic group. Specific examples of the anionic group include a carboxy group, a sulfonic acid group, a phosphoric acid group, a halogen group, a sulfate group and the like.
Specific examples of the compound having a carboxyl group include formic acid, acetic acid, propionic acid, butyric acid, and lactic acid.
Specific examples of the compound having a sulfonic acid group include ethane sulfonic acid and the like.
Specific examples of the compound having a phosphoric acid group include phosphoric acid and acidic phosphoric acid esters.
Specific examples of the compound having a halogen group include hydrochloric acid and the like.
Specific examples of the compound having a sulfuric acid group include sulfuric acid and the like.
Among them, as the compound having an anionic group, a compound having a carboxyl group is preferable, and acetic acid, propionic acid or butyric acid is more preferable.

(Hydrophilic compound with anionic hydrophilic group)
Specific examples of the anionic hydrophilic group include a carboxy group, a sulfonic acid group, a phosphoric acid group, a halogen group and a sulfate group.
Specific examples of the hydrophilic compound having an anionic hydrophilic group include compounds having both an anionic group and an active hydrogen group, and more specifically, for example, monohydroxycarboxylic acid and polyhydroxycarboxylic acid. Examples thereof include compounds having a carboxy group of an acid as an anionic group.
Examples of the monohydroxycarboxylic acid include 1-hydroxyacetic acid, 3-hydroxypropanoic acid, 12-hydroxy-9-octadecanoic acid, hydroxypivalic acid (hydroxypivalic acid), lactic acid and the like.
Examples of the compound having a carboxy group of the polyhydroxycarboxylic acid as an anionic group include dimethylol acetic acid, 2,2-dimethylol butyric acid, 2,2-dimethylol pentanoic acid, dihydroxysuccinic acid, dimethylol propionic acid and the like. ..
Further, a compound having a sulfonic acid group and an active hydrogen group in combination can be mentioned, and more specifically, for example, isethionic acid and the like can be mentioned.
Among them, hydroxypivalic acid or dimethylolpropionic acid is preferable as the compound having both an anionic group and an active hydrogen group.

The anionic hydrophilic group added to the blocked polyisocyanate is preferably neutralized with an amine compound which is a basic substance.
Specific examples of the amine compound include ammonia and water-soluble amino compounds.
Specific examples of the water-soluble amino compound include monoethanolamine, ethylamine, dimethylamine, diethylamine, triethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, triethanolamine, butylamine, dibutylamine, 2- Examples thereof include ethylhexylamine, ethylenediamine, propylenediamine, methylethanolamine, dimethylethanolamine, diethylethanolamine, morpholin and the like. Further, tertiary amines such as triethylamine and dimethylethanolamine can also be mentioned, and these can also be used. These amine compounds may be used alone or in combination of two or more.

<Anionic dispersant>
The blocked polyisocyanate composition of the present embodiment was mixed with an aqueous coating liquid by containing an anionic dispersant having a surface tension of 32 mN / m or more and 51 mN / m or less at 25 ° C. measured by the above measuring method. In some cases, the emulsifying property can be improved in water, and the water dispersion stability can be improved. Therefore, the storage stability of the resin composition can be improved. Dispersants capable of exerting this effect are anionic dispersants having a surface tension within the above range, and anionic dispersants, nonionic dispersants, cationic dispersants, and amphoteric dispersants having surface tensions outside the above range. Then, the present inventors have found for the first time that the effect cannot be sufficiently achieved.

The anionic dispersant used is not particularly limited as long as the surface tension at 25 ° C. measured by the above measuring method is 32 mN / m or more and 51 mN / m or less. Specifically, as the anionic dispersant, for example, a fatty acid salt type compound, an alkyl sulfate ester compound, a polyoxyethylene alkyl ether sulfate type compound, a polyoxyethylene alkyl ether sulfate type compound, and a polyoxyethylene polycyclic phenyl ether. Examples thereof include sulfate-type compounds, polyoxyalkylene alkenyl ether sulfate-type compounds, alkylbenzene sulfonate-type compounds, sulfosuccinate-type compounds, and alkyl phosphate-type compounds. Examples of the polyoxyethylene alkyl ether sulfate type compound include polyoxyethylene alkyl ether sulfate ammonium salt and polyoxyethylene alkyl ether sulfate sodium salt. Examples of the polyoxyethylene polycyclic phenyl ether sulfate type compound include polyoxyethylene polycyclic phenyl ether ammonium sulfate and polyoxyethylene polycyclic phenyl ether sodium sulfate. Examples of the polyoxyalkylene alkenyl ether sulfate type compound include polyoxyalkylene alkenyl ether ammonium sulfate. Of these, those having a surface tension at 25 ° C. of 32 mN / m or more and 51 mN / m or less can be used. Further, these anionic dispersants may be used alone or in combination of two or more.
Among these anionic dispersants, polyoxyethylene polycyclic phenyl ether ammonium sulfate, polyoxyethylene polycyclic phenyl ether sodium sulfate, polyoxyethylene alkyl ether ammonium sulfate, and polyoxyethylene alkyl ether sodium sulfate are particularly preferable. ..

The content of the anionic dispersant is preferably 0.01 parts by mass or more and 5 parts by mass or less, more preferably 0.05 parts by mass or more and 3 parts by mass or less, and 0.10 parts by mass with respect to 100 parts by mass of the blocked polyisocyanate. More than 2 parts by mass, more preferably 0.14 parts by mass or more and 1.6 parts by mass or less. When the content of the anionic dispersant is not less than the above lower limit value, the storage stability of the resin composition can be improved, while when it is not more than the above upper limit value, the resin can be obtained. The tensile strength when formed into a film can be made better.

<Carboxylate>
When the blocking agent contains (B) a compound having a heterocycle containing one or more nitrogens, the blocking polyisocyanate composition further contains a carboxylic acid salt.
Examples of the carboxylic acid salt include a quaternary ammonium salt of a carboxylic acid in which the counter cation is a quaternary ammonium ion, a carboxylic acid metal salt in which the counter cation is a metal ion, and the like, but from the viewpoint of low temperature curability. , Carboxylate metal salts are preferred.

Examples of the quaternary ammonium salt of the carboxylic acid (carboxylic acid salt of the quaternary ammonium cation) include those shown below.
(1) Acetates of tetraalkylammoniums such as tetramethylammonium, tetraethylammonium and tetrabutylammonium, and organic weak acid salts such as propionate, octylate, capricate, myristate and benzoate.
(2) Acetates such as aryltrialkylammonium such as benzyltrimethylammonium and trimethylphenylammonium, and organic weak acid salts such as propionate, octylate, capricate, myristate and benzoate.
(3) Acetates such as trimethylhydroxyethylammonium, trimethylhydroxypropylammonium, triethylhydroxyethylammonium, and triethylhydroxypropylammonium, and organic weak acids such as propionate, octylate, capricate, myristate, and benzoate. salt.

Metal species of carboxylic acid metal salts include sodium, potassium, lithium, cesium, nickel, cobalt, cadmium, barium, calcium, zinc, manganese, copper, cerium, zirconium, iron, lead, germanium, antimony, aluminum, titanium, etc. Bismus and the like can be mentioned. Among them, as the metal species, a monovalent metal is preferable from the viewpoint of storage stability of the blocked polyisocyanate composition. Further, from the viewpoint of low temperature curability, it is more preferable that it is a Group 1 element such as sodium, potassium, lithium and cesium.

The carboxylic acid of the carboxylic acid metal salt includes both monocarboxylic acid and dicarboxylic acid, for example, formic acid, acetic acid, acrylic acid, methacrylic acid, propionic acid, butyric acid, hexanoic acid, octyl acid, octanoic acid, capric acid, Examples thereof include aliphatic saturated acids such as stearate, oleic acid, eicosanoic acid, myristic acid and benzoic acid, unsaturated acids and aromatic acids. Among them, the carboxylic acid of the carboxylic acid metal salt is preferably one having 1 or more and 12 or less carbon atoms from the viewpoint of compatibility, and an aliphatic acid having 1 or more and 12 or less carbon atoms from the viewpoint of yellowing resistance of the coating film. More preferred.

Specific examples of the preferred metal carboxylic acid salt include sodium propionate, potassium acetate, potassium propionate, potassium 2-ethylhexanoate, cesium acetate, lithium acetate, bismuth 2-ethylhexanoate and the like. Is preferable.

From the viewpoint of storage stability of the blocked polyisocyanate composition, the content of the countercation of the carboxylate is preferably 0.1% by mass or more and 20% by mass or less, preferably 0.3% by mass or less, based on the total mass of the blocked polyisocyanate. It is more preferably mass% or more and 15 mass% or less, and further preferably 0.5 mass% or more and 10 mass% or less.
The content of the counter cation can be measured by an ion chromatograph after filtering the aqueous layer obtained by adding ultrapure water to the sample and mixing the sample with a filter. The measurement conditions are as shown in the examples.

<Other components>
The blocked polyisocyanate composition of the present embodiment may further contain an additive such as a solvent in addition to the blocked polyisocyanate and the anionic dispersant.

Examples of the solvent include 1-methylpyrrolidone, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-3-methyl-. 1-butanol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol dimethyl ether, methyl ethyl ketone, acetone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethanol, methanol, iso-propanol , 1-propanol, iso-butanol, 1-butanol, 2-ethylhexanol, cyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol , Ethyl acetate, isopropyl acetate, butyl acetate, toluene, xylene, pentane, iso-pentane, hexane, iso-hexane, cyclohexane, solvent naphtha, mineral spirit and the like. These solvents may be used alone or in combination of two or more. From the viewpoint of dispersibility in water, the solvent preferably has a solubility in water of 5% by mass or more, and specifically, dipropylene glycol monomethyl ether is preferable.

<Manufacturing method of blocked polyisocyanate composition>
The blocked polyisocyanate composition is not particularly limited, but is obtained, for example, by reacting the polyisocyanate with the blocking agent.
The blocking reaction between the polyisocyanate and the blocking agent can be carried out regardless of the presence or absence of a solvent, and a blocked polyisocyanate can be obtained.
As the blocking agent, one of (A) the compound (I) or (B) a compound having a heterocycle containing one or more nitrogen may be used alone, and the compound (I) or (B) may be used alone. ) Two or more kinds selected from compounds having a heterocycle containing one or more nitrogen may be used in combination, or the other blocking agents described above may be further used in combination.
The amount of the blocking agent added is usually 80 mol% or more and 200 mol% or less, preferably 90 mol% or more and 150 mol% or less, and 93 mol% or more and 130 mol% or less, based on the total molar amount of isocyanate groups. It is more preferably mol% or less.

When a solvent is used, a solvent that is inert to the isocyanate group may be used.
When a solvent is used, the content of the non-volatile content derived from the polyisocyanate and the blocking agent with respect to 100 parts by mass of the blocked polyisocyanate composition may be usually 10 parts by mass or more and 95 parts by mass or less, and 15 parts by mass or more and 80 parts by mass. It is preferably 20 parts by mass or less, and more preferably 20 parts by mass or more and 75 parts by mass or less.

In the blocking reaction, organic metal salts such as tin, zinc and lead, tertiary amine compounds and alkali metal alcoholates such as sodium may be used as catalysts.
The amount of the catalyst added varies depending on the temperature of the blocking reaction and the like, but is usually 0.05 parts by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of polyisocyanate, and 0.1 parts by mass. It is preferably 1.0 part by mass or less.

The blocking reaction can generally be carried out at −20 ° C. or higher and 150 ° C. or lower, preferably 0 ° C. or higher and 100 ° C. or lower, and more preferably 10 ° C. or higher and 70 ° C. or lower. When the temperature of the blocking reaction is at least the above lower limit value, the reaction rate can be further increased, and when it is at least the above upper limit value, the side reaction can be further suppressed.
After the blocking reaction, a neutralization treatment may be performed by adding an acidic compound or the like.
As the acidic compound, an inorganic acid may be used or an organic acid may be used. Examples of the inorganic acid include hydrochloric acid, phosphite, phosphoric acid and the like. Examples of the organic acid include methanesulfonic acid, p-toluenesulfonic acid, dioctylphthalate, dibutylphthalate and the like.

When a blocked polyisocyanate composition is produced by using a hydrophilic compound and a blocking agent, for example, it is obtained by reacting the polyisocyanate with the hydrophilic compound and the blocking agent.
The reaction of the isocyanate groups with the hydrophilic compound of a polyisocyanate, and, also possible to carry out the reaction of polyisocyanates with a blocking agent at the same time, or, after performing either of the reaction in advance, to perform a second reaction You can also. Above all, it is obtained after first reacting the isocyanate group with the hydrophilic compound to obtain a polyisocyanate composition modified with the hydrophilic compound (hereinafter, may be referred to as "modified polyisocyanate composition"). It is preferable to carry out the reaction between the modified polyisocyanate composition and the blocking agent.

The reaction between the polyisocyanate and the hydrophilic compound may use an organometallic salt, a tertiary amine compound, or an alkali metal alcoholate as a catalyst. Examples of the metal constituting the organometallic salt include tin, zinc, lead and the like. Examples of the alkali metal include sodium and the like.

The reaction temperature of the polyisocyanate and the hydrophilic compound is preferably −20 ° C. or higher and 150 ° C. or lower, and more preferably 30 ° C. or higher and 130 ° C. or lower. When the reaction temperature is equal to or higher than the above lower limit, the reactivity tends to be higher. Further, when the reaction temperature is equal to or lower than the above upper limit value, side reactions tend to be suppressed more effectively.

It is preferable to completely react with polyisocyanate so that the hydrophilic compound does not remain in an unreacted state. Since it does not remain in the unreacted state, it tends to more effectively suppress the water dispersion stability of the blocked polyisocyanate composition and the decrease in low temperature curability when formed into a resin film.

As the blocking reaction between the modified polyisocyanate composition and the blocking agent, the method described as the blocking reaction described above can be used.

≪Resin composition≫
The resin composition of the second embodiment of the present invention contains the block polyisocyanate composition of the first embodiment and a multivalent hydroxy compound. The resin composition of the present embodiment can also be said to be a one-component resin composition containing a curing agent component and a main component.

With the resin composition of the present embodiment, a resin film having excellent storage stability and excellent low-temperature curability can be obtained.
The constituent components of the resin composition of the present embodiment will be described in detail below.

<Multivalent hydroxy compound>
As used herein, the term "multivalent hydroxy compound" means a compound having at least two hydroxy groups (hydroxyl groups) in one molecule, and is also called a "polyol".
Specific examples of the polyvalent hydroxy compound include aliphatic hydrocarbon polyols, polyether polyols, polyester polyols, epoxy resins, fluorine-containing polyols, and acrylic polyols.
Among them, the polyvalent hydroxy compound is preferably polyester polyols, fluorine-containing polyols or acrylic polyols.

[Aliphatic hydrocarbon polyols]
Examples of the aliphatic hydrocarbon polyols include hydroxyl-terminated polybutadiene and hydrogenated additives thereof.

[Polyether polyols]
Examples of the polyether polyols include those obtained by using any of the following methods (1) to (3).
(1) Polyether polyols or polytetramethylene glycols obtained by adding a alkylene oxide alone or a mixture to a polyhydric alcohol alone or a mixture.
(2) Polyether polyols obtained by reacting an alkylene oxide with a polyfunctional compound.
(3) So-called polymer polyols obtained by polymerizing acrylamide or the like using the polyether polyols obtained in (1) or (2) as a medium.
Examples of the polyhydric alcohol include glycerin and propylene glycol.
Examples of the alkylene oxide include ethylene oxide and propylene oxide.
Examples of the polyfunctional compound include ethylenediamine and ethanolamines.

[Polyester polyols]
Examples of the polyester polyols include the polyester polyols according to any one of (1) and (2) below.
(1) Polyester polyol resins obtained by a condensation reaction between a dibasic acid alone or a mixture of two or more kinds and a polyhydric alcohol alone or a mixture of two or more kinds.
(2) Polycaprolactones obtained by ring-opening polymerization of ε-caprolactone with a polyhydric alcohol.
Examples of the dibasic acid include carboxylic acids such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic acid anhydride, isophthalic acid, terephthalic acid, and 1,4-cyclohexanedicarboxylic acid.
Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, trimethylolpropane, glycerin, and pentaerythritol. , 2-Methylolpropanediol, ethoxylated trimethylolpropane and the like.

[Epoxy resins]
Examples of the epoxy resins include novolak type epoxy resin, β-methylepicro type epoxy resin, cyclic oxylan type epoxy resin, glycidyl ether type epoxy resin, glycol ether type epoxy resin, epoxy type aliphatic unsaturated compound, and epoxidized fatty acid. Epoxy resins such as esters, ester-type polyvalent carboxylic acids, aminoglycidyl-type epoxy resins, halogenated epoxy resins, resorcin-type epoxy resins, and resins obtained by modifying these epoxy resins with amino compounds, polyamide compounds, etc. are mentioned. Be done.

[Fluorine-containing polyols]
Examples of the fluorine-containing polyols include fluoroolefins, cyclohexyl vinyl ethers, and hydroxys disclosed in Reference 1 (Japanese Patent Laid-Open No. 57-34107), Reference 2 (Japanese Patent Laid-Open No. 61-275311), and the like. Examples thereof include copolymers such as alkyl vinyl ether and monocarboxylic acid vinyl ester.

[Acrylic polyols]
The acrylic polyols are, for example, a polymerizable monomer having one or more active hydrogens in one molecule, or a polymerizable monomer having one or more active hydrogens in one molecule, and if necessary. , Is obtained by copolymerizing the polymerizable monomer with another copolymerizable monomer.

Examples of the polymerizable monomer having one or more active hydrogens in one molecule include those shown in (i) to (iii) below. These may be used individually by 1 type, and may be used in combination of 2 or more type.
(I) Acrylic acid esters having active hydrogen such as -2-hydroxyethyl acrylate, -2-hydroxypropyl acrylate, and -2-hydroxybutyl acrylate.
(Ii) Methacrylic acid esters having active hydrogen such as -2-hydroxyethyl methacrylate, -2-hydroxypropyl methacrylate, and -2-hydroxybutyl methacrylate.
(Iii) (meth) acrylic acid esters having polyvalent active hydrogen such as acrylic acid monoester or methacrylic acid monoester of glycerin, acrylic acid monoester or methacrylic acid monoester of trimethylpropan.

Examples of other monomers copolymerizable with the polymerizable monomer include those shown in (i) to (v) below. These may be used individually by 1 type, and may be used in combination of 2 or more type.
(I) Acrylic acid esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, -n-butyl acrylate, and -2-ethylhexyl acrylate.
(Ii) Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, -n-hexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, and glycidyl methacrylate. ..
(Iii) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid.
(Iv) Unsaturated amides such as acrylamide, N-methylolacrylamide, and diacetoneacrylamide.
(V) Styrene, vinyltoluene, vinyl acetate, acrylonitrile, etc.

Further, an acrylic polyol obtained by copolymerizing a polymerizable ultraviolet-stable monomer disclosed in Reference 3 (Japanese Patent Laid-Open No. 1-261409) and Reference 4 (Japanese Patent Laid-Open No. 3-006273). Kind and the like.

Specifically, as the polymerizable ultraviolet-stable monomer, for example, 4- (meth) acryloyloxy-2, 2,6,6-tetramethylpiperidin, 4- (meth) acryloylamino-2,2,6 , 6-Tetramethylpiperidin, 1-crotonoyl-4-crotonoyloxy-2, 2,6,6-tetramethylpiperidine, 2-hydroxy-4- (3-methacryloxy-2-hydroxypropoxy) benzophenone and the like. Be done.

For example, the above monomer component is solution-polymerized in the presence of a known radical polymerization initiator such as a peroxide or an azo compound, and if necessary, diluted with an organic solvent or the like to obtain an acrylic polyol. Can be done.

When an aqueous-based base acrylic polyol is obtained, it can be produced by a known method such as a method of solution-polymerizing an olefinically unsaturated compound to convert it into an aqueous layer or emulsion polymerization. In that case, water solubility or water dispersibility can be imparted by neutralizing an acidic portion such as a carboxylic acid-containing monomer such as acrylic acid or methacrylic acid or a sulfonic acid-containing monomer with amine or ammonia.

[NCO / OH]
The molar equivalent ratio (NCO / OH) of the isocyanate group of the blocked polyisocyanate composition to the hydroxyl group of the polyvalent hydroxy compound contained in the resin composition of the present embodiment is determined by the required physical properties of the resin film, but is usually determined. , 0.01 or more and 22.5 or less.

[Glass-transition temperature]
The glass transition temperature of the polyvalent hydroxy compound is preferably 0 ° C. or higher and 100 ° C. or lower, more preferably 0 ° C. or higher and 90 ° C. or lower, further preferably 0 ° C. or higher and 80 ° C. or lower, and particularly preferably 5 ° C. or higher and 70 ° C. or lower. When the glass transition temperature of the multivalent hydroxy compound is within the above range, a resin film having a higher tensile strength can be obtained. The glass transition temperature of the polyvalent hydroxy compound can be measured, for example, by using the method described in Examples described later.

[Weight average molecular weight]
The weight average molecular weight of polyhydroxy compound is preferably 5.0 × 10 ³ or more 2.0 × 10 ⁵ or less, more preferably 5.0 × 10 ³ or more 1.5 × 10 ⁵ or less, 5.0 × 10 ³ to 1.0 × 10 ⁵ or less it is more preferred. When the weight average molecular weight of the multivalent hydroxy compound is within the above range, a resin film having various physical properties such as tensile strength can be obtained. The weight average molecular weight of the polyvalent hydroxy compound is, for example, a polystyrene-based weight average molecular weight measured by gel permeation chromatography (GPC). Specifically, it can be measured by using the method described in Examples described later.

[Hydroxy group value]
The hydroxyl value of the multivalent hydroxy compound is preferably 30 mgKOH / g or more and 250 mgKOH / g or less, more preferably 40 mgKOH / g or more and 200 mgKOH / g or less, and further preferably 45 mgKOH / g or more and 180 mgKOH / g or less. When the hydroxyl value of the multivalent hydroxy compound is within the above range, a resin film having various physical properties such as tensile strength can be obtained. The hydroxyl value of the polyvalent hydroxy compound can be measured, for example, by using the method described in Examples described later.

The content of the blocked polyisocyanate in the resin composition of the present embodiment is preferably 5 parts by mass or more and 200 parts by mass or less, and more preferably 6 parts by mass or more and 180 parts by mass or less with respect to 100 parts by mass of the polyvalent hydroxy compound. It is more preferably 10 parts by mass or more and 150 parts by mass or less. When the content of the blocked polyisocyanate is within the above range, a resin film having various physical properties such as tensile strength can be obtained. The content of blocked polyisocyanate can be calculated, for example, from the blending amount, or identified and quantified using nuclear magnetic resonance (NMR) method and gas chromatography / mass spectrometry (GC / MS method). Can also be calculated.

<Other additives>
The resin composition of the present embodiment may further contain other additives.
Other additives include, for example, a curing agent capable of reacting with a crosslinkable functional group in a polyvalent hydroxy compound, a curing catalyst, a solvent, pigments (constituent pigments, coloring pigments, metallic pigments, etc.), ultraviolet absorbers, and photostabilizing agents. Examples thereof include agents, radical stabilizers, anti-yellowing agents that suppress coloration during the baking process, coating surface adjusting agents, flow adjusting agents, pigment dispersants, defoaming agents, thickening agents, and film forming aids.

Examples of the curing agent include melamine resin, urea resin, epoxy group-containing compound or resin, carboxyl group-containing compound or resin, acid anhydride, alkoxysilane group-containing compound or resin, hydrazide compound and the like.

The curing catalyst may be a basic compound or a Lewis acidic compound.
Examples of the basic compound include metal hydroxides, metal alkoxides, metal carboxylates, metal acetylacetylates, hydroxides of onium salts, onium carboxylates, halides of onium salts, and metal salts of active methylene compounds. Examples thereof include onium salts of active methylene compounds, aminosilanes, amines, phosphines and the like. As the onium salt, an ammonium salt, a phosphonium salt or a sulfonium salt is suitable.
Examples of the Lewis acidic compound include an organic tin compound, an organic zinc compound, an organic titanium compound, and an organic zirconium compound.

Examples of the solvent include those similar to those exemplified in the block polyisocyanate composition.

In addition, pigments (constitution pigments, coloring pigments, metallic pigments, etc.), ultraviolet absorbers, light stabilizers, radical stabilizers, anti-yellowing agents that suppress coloring during the baking process, coating surface conditioners, flow conditioners, pigments As the dispersant, antifoaming agent, thickener and film-forming auxiliary, known ones can be appropriately selected and used.

<Manufacturing method of resin composition>
The resin composition of the present embodiment can be used for both solvent-based and water-based bases, but the water-based base has good storage stability and excellent low-temperature curability at 80 ° C. or lower when formed into a resin film. Since the resin composition has not been known so far, it is preferably used as an aqueous-based resin composition.

When producing an aqueous-based resin composition (aqueous resin composition), first, a polyvalent hydroxy compound or an aqueous dispersion thereof or a water-soluble product is subjected to a crosslinkable functional group in the polyvalent hydroxy compound, if necessary. Curing agents, curing catalysts, solvents, pigments (constitution pigments, coloring pigments, metallic pigments, etc.), UV absorbers, light stabilizers, radical stabilizers, anti-yellowing agents that suppress coloring during the baking process, Add additives such as coating surface conditioner, flow conditioner, pigment dispersant, defoaming agent, thickener, and film-forming aid. Next, the blocked polyisocyanate composition or an aqueous dispersion thereof is added as a curing agent, and if necessary, water or a solvent is further added to adjust the viscosity. Then, the water-based resin composition (water-based resin composition) can be obtained by forcibly stirring with a stirring device.

When producing a solvent-based resin composition, first, a curing agent or curing catalyst capable of reacting with a polyvalent hydroxy compound or a solvent dilution thereof with a crosslinkable functional group in the polyvalent hydroxy compound, if necessary. , Solvents, pigments (constitution pigments, coloring pigments, metallic pigments, etc.), ultraviolet absorbers, light stabilizers, radical stabilizers, anti-yellowing agents that suppress coloring during the baking process, coating surface conditioners, flow conditioners, Add additives such as pigment dispersants, antifoaming agents, thickeners, and film-forming aids. Then, the block polyisocyanate composition is added as a curing agent, and if necessary, a solvent is further added to adjust the viscosity. Then, the solvent-based resin composition can be obtained by stirring by hand or using a stirring device such as a magella.

≪Resin film≫
The resin film of the third embodiment of the present invention is obtained by curing the resin composition of the second embodiment. The resin film of the present embodiment has good low-temperature curability.

The resin film of the present embodiment is obtained by coating the base material with the above resin composition by a known method such as roll coating, curtain flow coating, spray coating, bell coating, electrostatic coating, etc., and heating and curing. Obtained at.

From the viewpoint of energy saving and heat resistance of the base material, the heating temperature is preferably about 60 ° C. or higher and about 120 ° C. or lower, more preferably about 65 ° C. or higher and about 110 ° C. or lower, and further preferably about 70 ° C. or higher and about 100 ° C. or lower.
From the viewpoint of energy saving and heat resistance of the base material, the heating time is preferably about 1 minute or more and about 60 minutes or less, and more preferably about 2 minutes or more and about 40 minutes or less.

The base material is not particularly limited, and for example, the outer panel of an automobile body such as a passenger car, a truck, a motorcycle, or a bus; an automobile part such as a bumper; an outer panel of a household electric product such as a mobile phone or an audio device. Part: Various films and the like are mentioned, and among them, the outer panel part of the automobile body or the automobile part is preferable.

The material of the base material is not particularly limited, and is, for example, iron, aluminum, brass, copper, tin, stainless steel, zinc-plated steel, zinc alloy (Zn-Al, Zn-Ni, Zn-Fe, etc.) plating. Metallic materials such as steel; polyethylene resins, polypropylene resins, acrylonitrile-butadiene-styrene (ABS) resins, polyamide resins, acrylic resins, vinylidene chloride resins, polycarbonate resins, polyurethane resins, epoxy resins and other resins, various FRPs, etc. Examples include plastic materials; inorganic materials such as glass, cement and concrete; textile materials such as wood, paper and cloth, and among them, metal materials or plastic materials are preferable.

The base material is obtained by subjecting the surface of the metal material or the metal surface of a vehicle body or the like molded from the metal material to a surface treatment such as a phosphate treatment, a chromate treatment, or a composite oxide treatment. In addition, a coating film may be formed on the coating film. As the base material on which the coating film is formed, even if the base material is surface-treated as necessary and the undercoat coating film is formed on the base material, for example, the vehicle body in which the undercoat coating film is formed by the electrodeposition paint. Good. The base material may be a surface of the plastic material or a plastic surface of an automobile part or the like molded from the plastic material, which has been subjected to a desired surface treatment. Further, the base material may be a combination of a plastic material and a metal material.

As the resin film of the present embodiment, as shown in Examples described later, a resin film having a thickness of 40 μm obtained by heating and curing the resin composition at 80 ° C. for 30 minutes is stored at 23 ° C. for 1 week and then acetone. The gel fraction when immersed in the resin at 23 ° C. for 24 hours is preferably 80% by mass or more, more preferably 84% by mass or more, and further preferably 86% by mass or more. When the gel fraction is at least the above lower limit value, the low temperature curability can be improved. On the other hand, the upper limit of the gel fraction is not particularly limited, but may be, for example, 100% by mass. As a specific method for measuring the gel fraction, for example, the method shown in Examples described later can be used.

As shown in Examples described later, the resin film of the present embodiment has a resin film having a thickness of 40 μm, a width of 10 mm, and a length of 40 mm obtained by heating and curing the resin composition at 80 ° C. for 30 minutes between chucks. The maximum stress (tensile strength) in the tensile test conducted at a speed of 20 mm / min with the distance set to 20 mm is preferably 5 MPa or more, more preferably 10 MPa or more, and even more preferably 15 MPa or more. On the other hand, the upper limit of the maximum stress is not particularly limited, but can be, for example, 80 MPa, for example 70 MPa. As a specific method for measuring the maximum stress, for example, the method shown in Examples described later can be used.

Since the resin film of the present embodiment has excellent low-temperature curability, it is suitably used for products in various fields where energy saving is required and as a coating film for a material having low heat resistance.

≪Laminated body≫
The laminate of the fourth embodiment of the present invention contains two or more layers of the resin film of the third embodiment having different compositions. The thickness of the laminated body of the present embodiment per layer is 1 μm or more and 50 μm or less. The laminate of the present embodiment is excellent in low temperature curability by containing the above resin film.

The laminate of the present embodiment may include two or more layers of the above resin film having the same composition.

Further, the laminated body of the present embodiment is formed by laminating various coating films containing the resin film on the adherend.
Examples of the adherend include glass, various metals, porous members, various coated members, cured sealants, rubbers, leathers, fibers, non-woven fabrics, resin films and plates, and UV curing. Examples thereof include a mold acrylic resin layer and a layer made of inks. Examples of the various metals include aluminum, iron, galvanized steel sheet, copper, stainless steel and the like. Examples of the porous member include wood, paper, mortar, stone and the like. Examples of the various coatings include fluorine coating, urethane coating, acrylic urethane coating and the like. Examples of the cured sealant include silicone-based, modified silicone-based, urethane-based, and the like. Examples of the rubbers include natural rubber and synthetic rubber. Examples of the leathers include natural leathers and artificial leathers. Examples of the fibers include plant fibers, animal fibers, carbon fibers, glass fibers and the like. Examples of the resins used as raw materials for the films and plates of the resins include polyvinyl chloride, polyester, acrylic, polycarbonate, triacetyl cellulose, and polyolefin. Examples of the inks include printing inks and UV inks.

In the laminate of the present embodiment, the above resin compositions having different compositions are coated on the adherend by a known method such as roll coating, curtain flow coating, spray coating, bell coating, electrostatic coating, etc. It can be obtained by heating and curing each layer, or by heating and curing all the layers together after painting.

In addition to the resin film, the laminate of the present embodiment may include, for example, a layer composed of other known components such as a primer layer, an adhesive layer, and a decorative layer.

<< Hydrophilic polyisocyanate composition >>
The hydrophilic polyisocyanate composition of the fifth embodiment is derived from a hydrophilic compound and an alicyclic polyisocyanate having an isocyanurate group. That is, the hydrophilic polyisocyanate composition of the present embodiment contains a hydrophilic polyisocyanate which is a reaction product of a hydrophilic compound and an alicyclic polyisocyanate. The ratio of the isocyanate groups modified by the hydrophilic compound to the total molar amount of the isocyanate groups of the alicyclic polyisocyanate is 2 mol% or more and 15 mol% or less.

By having the above structure, the hydrophilic polyisocyanate composition of the present embodiment has good water dispersibility and excellent hardness when formed into a resin film.

The hydrophilic group is introduced by reacting the hydrophilic compound with the alicyclic isocyanate monomer or by reacting the hydrophilic compound with the alicyclic polyisocyanate. In the hydrophilic polyisocyanate composition of the present embodiment, the ratio of the isocyanate groups modified by the hydrophilic compound to the total molar amount of the isocyanate groups of the alicyclic polyisocyanate is the isocyanate group of the alicyclic polyisocyanate as a raw material. The ratio of the isocyanate group modified by the hydrophilic compound to 100 mol% (hereinafter, may be referred to as “modification rate”) can also be referred to as the isocyanate group into which the hydrophilic group has been introduced and the hydrophilic group. It can also be said that the ratio of the isocyanate group into which the hydrophilic group is introduced to the total molar amount of the isocyanate group into which is not introduced.
The modification rate is 2 mol% or more and 15 mol% or less, preferably 3 mol% or more and 14 mol% or less, more preferably 4 mol% or more and 12 mol% or less, and further preferably 5 mol% or more and 10 mol% or less.
When the modification rate is within the above range, the water dispersibility is good and the hardness of the resin film is excellent. Further, as shown in Examples described later, when the content is not less than the above lower limit value, the temperature is 80 ° C. or less when the hydrophilic polyisocyanate composition of the present embodiment is used as a blocked polyisocyanate composition as a resin film. It tends to be better in curability at low temperatures.
The denaturation rate can be measured using the following method. Specifically, unmodified alicyclic polyisocyanate, 1-modified alicyclic polyisocyanate, 2-modified alicyclic polyisocyanate, and 3-modified alicyclic polyisocyanate at 220 nm of liquid chromatography (LC). Obtained from the peak area ratio of isocyanate. The measuring device and measuring conditions can be, for example, as follows.

(Device and measurement conditions)
LC device: Waters, UPLC (trade name)
Column: ACQUITY UPLC HSS T3 1.8 μm manufactured by Waters
C18, inner diameter 2.1 mm x length 50 mm
Flow velocity: 0.3 mL / min
Mobile phase: A = 10 mM ammonium acetate aqueous solution, B = acetonitrile gradient condition: The initial mobile phase composition is A / B = 98/2, the ratio of B is linearly increased after sample injection, and A / after 10 minutes. B = 0/100.
Detection method: photodiode array detector, measurement wavelength 220 nm

Next, each component of the hydrophilic polyisocyanate composition of the present embodiment will be described in detail below.

<Alicyclic polyisocyanate>
The alicyclic polyisocyanate is a monomer compound having one or more isocyanate groups (-NCO) and having a skeleton composed of an alicyclic hydrocarbon group (hereinafter, referred to as "alicyclic isocyanate monomer"). It is a reactant obtained by reacting a plurality of (in some cases), and has an isocyanurate group. The "isocyanurate group" referred to here is a functional group formed by alkyne cuttering three isocyanate groups.
The alicyclic isocyanate monomer preferably has 4 or more and 30 or less carbon atoms. Specific examples of the alicyclic isocyanate monomer include isophorone diisocyanate (hereinafter, may be referred to as “IPDI”), 1,3-bis (diisocyanate methyl) cyclohexane, 4,4′-dicyclohexylmethane diisocyanate, and diisocyanate norbornane. , Di (isocyanet methyl) norbornane and other alicyclic diisocyanates. These alicyclic isocyanate monomers may be used alone or in combination of two or more. Among them, the alicyclic polyisocyanate is preferably a polyisocyanate having an isocyanurate group derived from IPDI.

The alicyclic polyisocyanate may have a functional group other than the isocyanurate group in addition to the isocyanurate group as long as the effect is not impaired, but it is preferable to have only the isocyanurate group. Examples of the functional group other than the isocyanurate group include an allophanate group, a uretdione group, an iminooxadiazinedione group, a urethane group, a biuret group and the like.

<Other polyisocyanates>
The hydrophilic polyisocyanate composition of the present embodiment may contain other polyisocyanates other than the alicyclic polyisocyanate as long as the effect is not impaired, but may contain only the alicyclic polyisocyanate. preferable.
Other polyisocyanates include monomer compounds having one or more isocyanate groups (-NCO) and having a skeleton composed of an aliphatic or aromatic hydrocarbon group (hereinafter, each "aliphatic isocyanate monomer"). Alternatively, it is a reactant obtained by reacting a plurality of (sometimes referred to as "aromatic isocyanate monomer"). Other polyisocyanates may or may not have an isocyanurate group.
Examples of the aliphatic isocyanate monomer include aliphatic diisocyanate and aliphatic triisocyanate. Examples of the aliphatic diisocyanate include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (hereinafter, may be referred to as “HDI”), and 2,2,4-trimethyl-1,6-diisocyanate. Natohexane, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 2-methylpentane-1,5-diisocyanate (MPDI), lysine diisocyanate (hereinafter, may be referred to as "LDI"), etc. Can be mentioned. Examples of the aliphatic triisocyanate include 4-isocyanate methyl-1,8-octamethylene diisocyanate (hereinafter, may be referred to as "NTI") and 1,3,6-hexamethylene triisocyanate (hereinafter, "HTI"). (Sometimes referred to as), bis (2-isocyanatoethyl) 2-isocyanatoglutarate (hereinafter sometimes referred to as “GTI”), lysine triisocyanate (hereinafter sometimes referred to as “LTI”), etc. Can be mentioned. Examples of the aromatic isocyanate monomer include diphenylmethane-4,4'-diisocyanate (MDI), 1,5-naphthalenediocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate, m-tetramethylxylylene diisocyanate (TMXDI) and the like. Aromatic diisocyanate of.

<Hydrophilic compound>
A hydrophilic compound is a compound having a hydrophilic group. In addition to the hydrophilic group, the hydrophilic compound preferably has at least one active hydrogen group for reacting with at least one of the isocyanate groups of the alicyclic polyisocyanate with respect to one molecule of the hydrophilic compound. .. Specific examples of the active hydrogen group include a hydroxyl group, a mercapto group, a carboxylic acid group, an amino group, and a thiol group.

Examples of the hydrophilic compound include a nonionic compound, a cationic compound, and an anionic compound. These hydrophilic compounds may be used alone or in combination of two or more. Among them, as the hydrophilic compound, a nonionic compound is preferable from the viewpoint of easy availability and less susceptible to electrical interaction with the formulation, and an anionic compound is preferable from the viewpoint of suppressing a decrease in hardness of the obtained resin film. Compounds are preferred.

(Nonionic compound)
Specific examples of the nonionic compound include monoalcohols and compounds in which ethylene oxide is added to the hydroxyl groups of alcohols. Examples of the monoalcohol include methanol, ethanol, butanol and the like. Examples of the compound in which ethylene oxide is added to the hydroxyl group of the alcohol include ethylene glycol, diethylene glycol, polyethylene glycol, polyethylene glycol monomethyl ether and the like. These nonionic compounds also have an active hydrogen group that reacts with an isocyanate group.
Among them, as the nonionic compound, polyethylene glycol monoalkyl ether in which ethylene oxide is added to the hydroxyl group of the monoalcohol is preferable because the water dispersibility of the hydrophilic polyisocyanate composition can be improved with a small amount of use.

The number of ethylene oxides added to the compound to which ethylene oxide is added is preferably 4 or more and 30 or less, and more preferably 4 or more and 25 or less. When the number of ethylene oxides added is not less than the above lower limit, water dispersibility tends to be more effectively imparted to the hydrophilic polyisocyanate composition, and when the number of ethylene oxides added is not more than the above upper limit. , Precipitates of hydrophilic polyisocyanate compositions tend to be less likely to occur during low temperature storage.

The lower limit of the amount of nonionic hydrophilic groups added to the alicyclic polyisocyanate (hereinafter, may be referred to as "content of nonionic hydrophilic groups") is the water dispersion stability of the hydrophilic polyisocyanate composition. From the viewpoint of properties, 1% by mass is preferable, 2% by mass is more preferable, 3% by mass is more preferable, and 4% by mass is particularly preferable with respect to the mass of the solid content of the hydrophilic polyisocyanate composition.
The upper limit of the content of the nonionic hydrophilic group is preferably 55% by mass, preferably 50% by mass, based on the mass of the solid content of the hydrophilic polyisocyanate composition from the viewpoint of water resistance of the obtained resin film. Is more preferable, 48% by mass is further preferable, and 44% by mass is particularly preferable.
That is, the content of the nonionic hydrophilic group is preferably 1% by mass or more and 55% by mass or less, more preferably 2% by mass or more and 50% by mass or less, based on the mass of the solid content of the hydrophilic polyisocyanate composition. It is more preferably 3% by mass or more and 48% by mass or less, and particularly preferably 4% by mass or more and 44% by mass or less.
When the content of the nonionic hydrophilic group is within the above range, the hydrophilic polyisocyanate composition is more dispersed in water, and a homogeneous film tends to be obtained.

(Cationic compound)
Specific examples of the cationic compound include a compound having both a cationic hydrophilic group and an active hydrogen group. Further, a compound having an active hydrogen group such as a glycidyl group and a compound having a cationic hydrophilic group such as sulfide and phosphine may be combined to form a hydrophilic compound. In this case, a compound having an isocyanate group and a compound having an active hydrogen group are reacted in advance to add a functional group such as a glycidyl group, and then a compound such as sulfide or phosphine is reacted. From the viewpoint of ease of production, a compound having both a cationic hydrophilic group and an active hydrogen group is preferable.

Specific examples of the compound having both a cationic hydrophilic group and an active hydrogen group include dimethylethanolamine, diethylethanolamine, diethanolamine, methyldiethanolamine and the like. Further, the tertiary amino group added using these compounds can be quaternized with, for example, dimethyl sulfate or diethyl sulfate.

The reaction of the cationic compound with the alicyclic polyisocyanate can be carried out in the presence of a solvent. The solvent in this case is preferably one that does not contain an active hydrogen group, and specific examples thereof include ethyl acetate, propylene glycol monomethyl ether acetate, and dipropylene glycol dimethyl ether.

The cationic hydrophilic group added to the alicyclic polyisocyanate is preferably neutralized with a compound having an anionic group. Specific examples of the anionic group include a carboxy group, a sulfonic acid group, a phosphoric acid group, a halogen group, a sulfate group and the like.
Specific examples of the compound having a carboxyl group include formic acid, acetic acid, propionic acid, butyric acid, and lactic acid.
Specific examples of the compound having a sulfonic acid group include ethane sulfonic acid and the like.
Specific examples of the compound having a phosphoric acid group include phosphoric acid and acidic phosphoric acid esters.
Specific examples of the compound having a halogen group include hydrochloric acid and the like.
Specific examples of the compound having a sulfuric acid group include sulfuric acid and the like.
Among them, as the compound having an anionic group, a compound having a carboxyl group is preferable, and acetic acid, propionic acid or butyric acid is more preferable.

(Anionic compound)
Specific examples of the anionic hydrophilic group include a carboxy group, a sulfonic acid group, a phosphoric acid group, a halogen group and a sulfate group.
Specific examples of the anionic compound include compounds having both an anionic group and an active hydrogen group. More specifically, for example, the carboxy group of a monohydroxycarboxylic acid or a polyhydroxycarboxylic acid is anionic. Examples include compounds having as a group.
Examples of the monohydroxycarboxylic acid include 1-hydroxyacetic acid, 3-hydroxypropanoic acid, 12-hydroxy-9-octadecanoic acid, hydroxypivalic acid (hydroxypivalic acid), lactic acid and the like.
Examples of the compound having a carboxy group of the polyhydroxycarboxylic acid as an anionic group include dimethylol acetic acid, 2,2-dimethylol butyric acid, 2,2-dimethylol pentanoic acid, dihydroxysuccinic acid, dimethylol propionic acid and the like. ..
Further, a compound having a sulfonic acid group and an active hydrogen group in combination can be mentioned, and more specifically, for example, isethionic acid and the like can be mentioned.
Among them, hydroxypivalic acid or dimethylolpropionic acid is preferable as the compound having both an anionic group and an active hydrogen group.

The anionic hydrophilic group added to the alicyclic polyisocyanate is preferably neutralized with an amine compound which is a basic substance.
Specific examples of the amine compound include ammonia and water-soluble amino compounds.
Specific examples of the water-soluble amino compound include monoethanolamine, ethylamine, dimethylamine, diethylamine, triethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, triethanolamine, butylamine, dibutylamine, 2- Examples thereof include ethylhexylamine, ethylenediamine, propylenediamine, methylethanolamine, dimethylethanolamine, diethylethanolamine, morpholin and the like. Further, tertiary amines such as triethylamine and dimethylethanolamine can also be mentioned, and these can also be used. These amine compounds may be used alone or in combination of two or more.

<Method for producing hydrophilic polyisocyanate composition>
The method for producing the hydrophilic polyisocyanate composition of the present embodiment is not particularly limited, but (i) after prepolymerizing the alicyclic isocyanate monomer, the obtained prepolymer is reacted with the hydrophilic compound. Examples thereof include a method (ii) of reacting an alicyclic isocyanate monomer with a hydrophilic compound. Above all, the method (i) above is preferable.

As a method of prepolymerizing the alicyclic isocyanate monomer to obtain a prepolymer having an isocyanurate group, for example, an isocyanurate-forming reaction catalyst can be used.

The isocyanurate-forming reaction catalyst is not particularly limited, but is generally preferably one having basicity. Specific examples of the isocyanurate-forming reaction catalyst include those shown below.
1) Hydrooxides of tetraalkylammoniums such as tetramethylammonium, tetraethylammonium, and tetrabutylammonium, and acetates, propionates, octylates, capricates, myristates, and benzoates of the tetraalkylammonates. Organic weak salts such as.
2) Hydroxide of aryltrialkylammonium such as benzyltrimethylammonium and trimethylphenylammonium, and acetate, propionate, octylate, capricate, myristate, benzoate and the like of the aryltrialkylammonium. Organic ammonium salt.
3) Hydroxide of hydroxyalkylammonium such as trimethylhydroxyethylammonium, trimethylhydroxypropylammonium, triethylhydroxyethylammonium, triethylhydroxypropylammonium, and acetate, propionate, octylate, capric acid of the hydroxyalkylammonium. Organic weak acid salts such as salts, myristates, and benzoates.
4) Metal salts of alkylcarboxylic acids such as acetic acid, propionic acid, caproic acid, octyl acid, caproic acid and myristic acid such as tin, zinc and lead.
5) Metalal alcoholates such as sodium and potassium.
6) Aminosilyl group-containing compound such as hexamethylene disilazane.
7) Mannich bases.
8) A mixture of tertiary amines and an epoxy compound.
9) Phosphorus compounds such as tributylphosphine.

Among them, from the viewpoint of less likely to generate unnecessary by-products, the isocyanurate-forming reaction catalyst is preferably a quaternary ammonium hydrooxide or a quaternary ammonium organic weak acid salt, and a tetraalkylammonium hydrooxide, More preferably, it is an organic weakened salt of tetraalkylammonium, a hydroxide of aryltrialkylammonium, or an organic weakened salt of aryltrialkylammonium.

The upper limit of the amount of the isocyanurate-forming reaction catalyst used is preferably 1000 mass ppm, more preferably 500 mass ppm, and 100 mass ppm with respect to the mass of the charged alicyclic isocyanate monomer. Is more preferable.
On the other hand, the lower limit of the amount of the isocyanurate-forming reaction catalyst used is not particularly limited, but may be, for example, 10 mass ppm.

The isocyanurate-forming reaction temperature is preferably 50 ° C. or higher and 120 ° C. or lower, and more preferably 55 ° C. or higher and 90 ° C. or lower. When the isocyanurate-forming reaction temperature is not more than the above upper limit value, coloring of the prepolymer tends to be suppressed more effectively.

When the desired conversion rate (the ratio of the mass of the prepolymer produced by the isocyanurate-forming reaction to the mass of the charged alicyclic isocyanate monomer) is reached, the isocyanurate-forming reaction is carried out with an acidic compound (for example, phosphoric acid, etc.). It is stopped by the addition of (acidic phosphate ester, etc.).
In order to obtain a prepolymer, it is necessary to stop the progress of the reaction at an early stage. However, since the initial reaction rate of the isocyanurate-forming reaction is very fast, it is difficult to stop the progress of the reaction at the initial stage, and the reaction conditions, particularly the amount and method of addition of the catalyst must be carefully selected. is there. For example, a method of dividing and adding the catalyst at regular time intervals is recommended as a suitable method.
Therefore, the conversion rate of the isocyanurate-forming reaction for obtaining the prepolymer is preferably 10% or more and 60% or less, more preferably 15% or more and 55% or less, and 20% or more and 50% or less. Is even more preferable.
When the conversion rate of the isocyanurate-forming reaction is not more than the above upper limit value, the hydrophilic polyisocyanate composition can have a lower viscosity. Further, when the conversion rate of the isocyanurate-forming reaction is at least the above lower limit value, the reaction stop operation can be performed more easily.

Further, when inducing a prepolymer containing an isocyanurate group, an alcohol having a valence of 1 or more and 6 or less can be used in addition to the alicyclic isocyanate monomer.
Examples of the monohydric or higher and hexavalent or lower alcohols that can be used include non-polymerizable alcohols and polymerizable alcohols. The term "non-polymerizable alcohol" as used herein means an alcohol having no polymerizable group. On the other hand, the "polymerizable alcohol" means an alcohol obtained by polymerizing a monomer having a polymerizable group and a hydroxyl group.
Examples of the non-polymerizable alcohol include polyhydric alcohols such as monoalcohols, diols, triols and tetraols.
Examples of monoalcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, n-pentanol, n-hexanol, n-octanol, n-nonanol, and 2-ethylbutanol. , 2,2-Dimethylhexanol, 2-ethylhexanol, cyclohexanol, methylcyclohexanol, ethylcyclohexanol and the like.
Examples of diols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, and 1, 3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol, 2-methyl-2,3-butanediol, 1, 6-Hexanediol, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, 2-ethyl-hexanediol, 1,2-octanediol, 1,2-decanediol, 2,2,4-trimethylpentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propane Examples include diol.
Examples of triols include glycerin, trimethylolpropane and the like.
Examples of tetraols include pentaerythritol and the like.

The polymerizable alcohol is not particularly limited, and examples thereof include polyester polyols, polyether polyols, acrylic polyols, and polyolefin polyols.

The polyester polyols are not particularly limited, and examples thereof include products obtained by a condensation reaction between a dibasic acid alone or a mixture and a polyhydric alcohol alone or a mixture.
The dibasic acid is not particularly limited, but is at least one selected from the group consisting of carboxylic acids such as succinic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride, phthalic acid anhydride, isophthalic acid, and terephthalic acid. Species of dibasic acid.
The polyhydric alcohol is not particularly limited, and examples thereof include at least one polyhydric alcohol selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, trimethylolpropane, and glycerin.
Examples of polyester polyols include polycaprolactones obtained by ring-opening polymerization of ε-caprolactone using the above-mentioned polyhydric alcohol.

The polyether polyols are not particularly limited, but for example, an alkali metal hydroxide or a strongly basic catalyst is used to add an alkylene oxide alone or a mixture to a polyhydric alcohol alone or a mixture. Examples thereof include polyether polyols obtained by reacting a polyamine compound with an alkylene oxide, and so-called polymer polyols obtained by polymerizing acrylamide or the like using the above-mentioned polyethers as a medium.
Examples of the alkali metal include lithium, sodium, potassium and the like.
Examples of the strong basic catalyst include alcoholates and alkylamines.
Examples of the polyhydric alcohol include those similar to those exemplified in the above polyester polyols.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide and the like.
Examples of the polyamine compound include ethylenediamines.

The acrylic polyols are not particularly limited, but for example, an ethylenically unsaturated bond-containing monomer having a hydroxyl group alone or a mixture thereof and another ethylenically unsaturated bond-containing monomer copolymerizable therewith are used alone. Alternatively, a copolymer of a mixture may be used.
The ethylenically unsaturated bond-containing monomer having a hydroxyl group is not particularly limited, and is, for example, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyhydroxymethacrylate. Butyl and the like can be mentioned.
The other ethylenically unsaturated bond-containing monomer copolymerizable with the ethylenically unsaturated bond-containing monomer having a hydroxyl group is not particularly limited, and is, for example, an acrylic acid ester, a methacrylic acid ester, or an unsaturated carboxylic acid. , Unsaturated amides, vinyl-based monomers, and vinyl-based monomers having a hydrolyzable silyl group.
Examples of the acrylic acid ester include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, -n-butyl acrylate, isobutyl acrylate, -n-hexyl acrylate, cyclohexyl acrylate, and -2 acrylate. -Ethylhexyl, lauryl acrylate, benzyl acrylate, phenyl acrylate and the like can be mentioned.
Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, -n-hexyl methacrylate, cyclohexyl methacrylate, and -2 methacrylic acid. -Ethylhexyl, lauryl methacrylate, benzyl methacrylate, phenyl methacrylate and the like can be mentioned.
Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, itaconic acid and the like.
Examples of unsaturated amides include acrylamide, methacrylamide, N, N-methylenebisacrylamide, diacetoneacrylamide, diacetonemethacrylamide, maleic acid amide, and maleimide.
Examples of the vinyl-based monomer include glycidyl methacrylate, styrene, vinyltoluene, vinyl acetate, acrylonitrile, dibutyl fumarate and the like.
Examples of the vinyl-based monomer having a hydrolyzable silyl group include vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, and the like.

Examples of polyolefin polyols include hydroxyl-terminated polybutadiene and hydrogenated products thereof.

The unreacted alicyclic isocyanate monomer can be removed from the reaction solution after completion of the reaction by thin film distillation, extraction or the like to obtain a prepolymer.

The reaction between the prepolymer and the hydrophilic compound may use an organometallic salt, a tertiary amine compound, or an alkali metal alcoholate as a catalyst. Examples of the metal constituting the organometallic salt include tin, zinc, lead and the like. Examples of the alkali metal include sodium and the like.

The reaction temperature of the prepolymer and the hydrophilic compound is preferably −20 ° C. or higher and 150 ° C. or lower, and more preferably 30 ° C. or higher and 130 ° C. or lower. When the reaction temperature is equal to or higher than the above lower limit, the reactivity tends to be higher. Further, when the reaction temperature is equal to or lower than the above upper limit value, side reactions tend to be suppressed more effectively.

It is preferable to completely react with the prepolymer so that the hydrophilic compound does not remain in an unreacted state. Since it does not remain in the unreacted state, the water dispersibility of the hydrophilic polyisocyanate composition can be improved.

<Characteristics of hydrophilic polyisocyanate composition>
[Average number of functional groups of isocyanate groups]
In the hydrophilic polyisocyanate composition of the present embodiment, the average number of functional groups of the alicyclic polyisocyanate before hydrophilization (before modification with a hydrophilic compound), that is, the alicyclic polyisocyanate as a raw material is 2. It is preferably 5.5 or more and 6.0 or less, more preferably 2.7 or more and 5.8 or less, and further preferably 2.9 or more and 5.5 or less.
When the average number of functional groups is within the above range, the hardness of the resin film tends to be further increased.
The average number of functional groups can be measured by using the method described in Examples described later.

[Weight average molecular weight]
The weight average molecular weight (Mw) of the hydrophilic polyisocyanate composition is preferably 900 or more and 20,000 or less, more preferably 1200 or more and 18,000 or less, and further preferably 1300 or more and 17,000 or less.
When the weight average molecular weight is within the above range, the water dispersibility is good and the hardness of the resin film is excellent.
The weight average molecular weight can be measured using the method described in Examples described later.

≪Block polyisocyanate composition≫
The blocked polyisocyanate composition of the sixth embodiment is formed by sealing at least a part of the isocyanate groups in the hydrophilic polyisocyanate composition with a blocking agent.
Above all, it is preferable that all the isocyanate groups in the hydrophilic polyisocyanate composition are sealed with a blocking agent. It can be confirmed by, for example, Fourier transform infrared spectroscopy (FT-IR) that all the isocyanate groups are sealed with the blocking agent by the disappearance of absorption due to isocyanate.
Further, the blocked polyisocyanate composition of the present embodiment has the above-mentioned hydrophilic group introduced into the alicyclic polyisocyanate having an isocyanurate group (hereinafter, may be referred to as "water-dispersible polyisocyanate"). In addition, if it has an alicyclic polyisocyanate in which a hydrophilic group has not been introduced (hereinafter, may be referred to as "unintroduced alicyclic polyisocyanate") or other polyisocyanate, any of the polyisocyanates It is preferable that the isocyanate group is also sealed with a blocking agent. The blocking agents for sealing the isocyanate groups of water-dispersible polyisocyanates, unintroduced alicyclic polyisocyanates and other polyisocyanates may be the same or different, but are preferably the same.

Since the blocked polyisocyanate composition of the present embodiment is derived from the above hydrophilic polyisocyanate composition, it has good water dispersibility, and has a hardness and low temperature curability when formed into a resin film. Excellent.

Each component of the blocked polyisocyanate composition of the present embodiment will be described in detail below. The hydrophilic polyisocyanate composition is as described above.

<Blocking agent>
The blocking agent is not particularly limited, and specific examples thereof include a compound having one active hydrogen in the molecule. Such a blocking agent is not particularly limited, but specifically, an alcohol compound, an alkylphenol compound, a phenol compound, an active methylene compound, a mercaptan compound, an acid amide compound, an acid imide compound, and an imidazole. Examples thereof include system compounds, urea compounds, oxime compounds, amine compounds, imine compounds, pyrazole compounds, and triazole compounds. These blocking agents may be used alone or in combination of two or more. A more specific example of the blocking agent is shown below.

The alcohol-based compound is not particularly limited, but specifically, for example, methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxy. Examples thereof include ethanol and 2-butoxyethanol.

The alkylphenol-based compound is not particularly limited, and specific examples thereof include mono and dialkylphenols having an alkyl group having 4 or more carbon atoms as a substituent. Examples of monoalkylphenols include n-propylphenol, iso-propylphenol, n-butylphenol, sec-butylphenol, tert-butylphenol, n-hexylphenol, 2-ethylhexylphenol, n-octylphenol, n-nonylphenol and the like. Be done. Examples of dialkylphenols include di-n-propylphenol, diisopropylphenol, isopropylcresol, di-n-butylphenol, di-tert-butylphenol, di-sec-butylphenol, di-n-octylphenol, and di-2-ethylhexyl. Examples thereof include phenol and di-n-nonylphenol.

The phenolic compound is not particularly limited, and specific examples thereof include phenol, cresol, ethylphenol, styrenated phenol, and hydroxybenzoic acid ester.

The active methylene compound is not particularly limited, and specific examples thereof include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, and ethyl isobutanoyl acetate.

The mercaptan-based compound is not particularly limited, and specific examples thereof include butyl mercaptan and dodecyl mercaptan.

The acid amide compound is not particularly limited, and specific examples thereof include acetanilide, acetate amide, ε-caprolactam, δ-valerolactam, and γ-butyrolactam.

The acidimide-based compound is not particularly limited, and specific examples thereof include succinimide and maleateimide.

The imidazole compound is not particularly limited, and specific examples thereof include imidazole and 2-methylimidazole.

The urea-based compound is not particularly limited, and specific examples thereof include urea, thiourea, and ethylene urea.

The oxime-based compound is not particularly limited, and specific examples thereof include formaldehyde, acetaldoxime, acetoxime, methylethylketooxime, and cyclohexanone oxime.

The amine compound is not particularly limited, and specific examples thereof include diphenylamine, aniline, carbazole, di-n-propylamine, diisopropylamine, and isopropylethylamine.

The imine-based compound is not particularly limited, and specific examples thereof include ethyleneimine and polyethyleneimine.

The pyrazole-based compound is not particularly limited, and specific examples thereof include pyrazole, 3-methylpyrazole, and 3,5-dimethylpyrazole.

The triazole-based compound is not particularly limited, and specific examples thereof include 1,2,4-triazole, 1,2,3-triazole and the like.

Among them, active methylene compounds, oxime compounds, amine compounds, pyrazole compounds, or triazole compounds are preferable in terms of availability, viscosity of the obtained blocked polyisocyanate composition, curing temperature, and curing time, and resins are preferable. Diisopropyl malate or di-tert-butyl malate is particularly preferable because the film is particularly excellent in curability at a low temperature of about 80 ° C. or lower.

<Manufacturing method of blocked polyisocyanate composition>
The blocked polyisocyanate composition is not particularly limited, but is obtained, for example, by reacting the hydrophilic polyisocyanate composition with the blocking agent.
The blocking reaction between the hydrophilic polyisocyanate composition and the blocking agent can be carried out regardless of the presence or absence of a solvent, and a blocked polyisocyanate composition is obtained.
As the blocking agent, one type may be used alone, or two or more types may be used in combination.
The amount of the blocking agent added is usually 80 mol% or more and 200 mol% or less, preferably 90 mol% or more and 150 mol% or less, and 93 mol% or more and 130 mol% or less, based on the total molar amount of isocyanate groups. It is more preferably mol% or less.

When a solvent is used, a solvent that is inert to the isocyanate group may be used.
When a solvent is used, the content of the solid content derived from the hydrophilic polyisocyanate composition and the blocking agent with respect to 100 parts by mass of the blocked polyisocyanate composition may be usually 10 parts by mass or more and 95 parts by mass or less. It is preferably 20 parts by mass or more and 80 parts by mass or less, and more preferably 20 parts by mass or more and 75 parts by mass or less.

In the blocking reaction, organic metal salts such as tin, zinc and lead, tertiary amine compounds and alkali metal alcoholates such as sodium may be used as catalysts.
The amount of the catalyst added varies depending on the temperature of the blocking reaction and the like, but is usually 0.05 parts by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of polyisocyanate, and 0.05 parts by mass. It is preferably 1.0 part by mass or less.

The blocking reaction can generally be carried out at −20 ° C. or higher and 150 ° C. or lower, preferably 0 ° C. or higher and 100 ° C. or lower, and more preferably 10 ° C. or higher and 90 ° C. or lower. When the temperature of the blocking reaction is at least the above lower limit value, the reaction rate can be further increased, and when it is at least the above upper limit value, the side reaction can be further suppressed.
After the blocking reaction, a neutralization treatment may be performed by adding an acidic compound or the like.
As the acidic compound, an inorganic acid may be used or an organic acid may be used. Examples of the inorganic acid include hydrochloric acid, phosphite, phosphoric acid and the like. Examples of the organic acid include methanesulfonic acid, p-toluenesulfonic acid, dioctylphthalate, dibutylphthalate and the like.

≪Resin composition≫
The resin composition of the seventh embodiment contains the hydrophilic polyisocyanate composition of the fifth embodiment or the blocked polyisocyanate composition of the sixth embodiment, and a polyol.

The resin composition of the present embodiment is excellent in hardness when made into a resin film by containing the above-mentioned hydrophilic polyisocyanate composition as a curing agent component. Further, the resin composition of the present embodiment is excellent in hardness when formed into a resin film and curability at a low temperature of about 80 ° C. or less by containing the block polyisocyanate composition.

The constituent components of the resin composition of the present embodiment will be described in detail below. The hydrophilic polyisocyanate composition and the blocked polyisocyanate composition are as described above.

<Polyol>
Examples of the polyol include polyester polyol, polyether polyol, acrylic polyol, polyolefin polyol, fluorine polyol, polycarbonate polyol, polyurethane polyol and the like. These polyols may be contained alone or in combination of two or more.
Among them, as the polyol, polyester polyol, acrylic polyol, or a mixture thereof is preferable.

[Polyester polyol]
The polyester polyol can be obtained, for example, by subjecting a dibasic acid alone or a mixture of two or more kinds to a condensation reaction of a polyhydric alcohol alone or a mixture of two or more kinds.

Examples of the dibasic acid include carboxylic acids such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic acid anhydride, isophthalic acid, terephthalic acid, and 1,4-cyclohexanedicarboxylic acid.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, trimethylolpropane, glycerin, and pentaerythritol. , 2-Methylolpropanediol, ethoxylated trimethylolpropane and the like.

Alternatively, for example, polycaprolactones obtained by ring-opening polymerization of lactones such as ε-caprolactone with a polyhydric alcohol can also be used as the polyester polyol.

[Polyether polyol]
The polyether polyols are not particularly limited, and examples thereof include those shown in (1) to (3) below.

(1) Polyether polyols obtained by randomly or blocking addition of a alkylene oxide alone or a mixture to a polyvalent hydroxy compound alone or a mixture using a catalyst.
Examples of the catalyst include hydroxides (lithium, sodium, potassium, etc.), strong basic catalysts (alcolate, alkylamine, etc.), complex metallic cyanide complex (metal porphyrin, zinc hexacyanocobalate complex, etc.) and the like. Be done.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, and styrene oxide.
(2) Polyether polyols obtained by reacting a polyamine compound with an alkylene oxide.
Examples of the polyamine compound include ethylenediamines.
Examples of the alkylene oxide include those similar to those exemplified in (1).
(3) So-called polymer polyols obtained by polymerizing acrylamide or the like using the polyether polyols obtained in (1) or (2) as a medium.

Examples of the multivalent hydroxy compound include those shown in the following (i) to (vi).
(I) Diglycerin, ditrimethylolpropane, pentaerythritol, dipentaerythritol, etc.
(Ii) Sugar alcohol compounds such as erythritol, D-threitol, L-arabinitol, ribitol, xylitol, sorbitol, mannitol, galactitol, and ramnitol.
(Iii) Monosaccharides such as arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, rhamnose, fucose, and ribodesose.
(Iv) Disaccharides such as trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, and melibiose.
(V) Trisaccharides such as raffinose, gentianose, and meletitose.
(Vi) Tetrasaccharides such as stachyose.

[Acrylic polyol]
The acrylic polyol is not particularly limited, but for example, an ethylenically unsaturated bond-containing monomer having a hydroxy group alone or a mixture thereof and another ethylenically unsaturated bond-containing monomer copolymerizable therewith are used alone. Alternatively, those obtained by copolymerizing with a mixture can be mentioned.

The ethylenically unsaturated bond-containing monomer having a hydroxy group is not particularly limited, and for example, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and methacryl. Hydroxybutyl acid acid and the like can be mentioned. These may be used alone or in combination of two or more types. Of these, hydroxyethyl acrylate or hydroxyethyl methacrylate is preferable.

Examples of other ethylenically unsaturated bond-containing monomers copolymerizable with the above-mentioned monomers include those shown in the following (1) to (6). These may be used alone or in combination of two or more types.

(1) Methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, -n-butyl acrylate, isobutyl acrylate, -n-hexyl acrylate, cyclohexyl acrylate, -2-ethylhexyl acrylate, acrylate Acrylic acid esters such as lauryl, benzyl acrylate, phenyl acrylate, -2-methoxyethyl acrylate, ethoxyethyl acrylate, methoxy-polyethylene glycol acrylate.
(2) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, -n-hexyl methacrylate, cyclohexyl methacrylate, -2-ethylhexyl methacrylate, methacrylic acid Methacrylic acid esters such as lauryl, benzyl methacrylate, and phenyl methacrylate.
(3) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid.
(4) Unsaturated amides such as acrylamide, methacrylamide, N, N-methylenebisacrylamide, diacetoneacrylamide, diacetonemethacrylamide, maleic acid amide, and maleimide.
(5) Vinyl-based monomers such as glycidyl methacrylate, styrene, vinyltoluene, vinyl acetate, acrylonitrile, and dibutyl fumarate.
(6) A vinyl-based monomer having a hydrolyzable silyl group such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, and γ- (meth) acryloxypropyltrimethoxysilane.

[Polyolefin polyol]
The polyolefin polyol is not particularly limited, and examples thereof include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, and hydrogenated polyisoprene.

It is preferable that the number of hydroxyl groups (hereinafter, may be referred to as “average number of hydroxyl groups”) possessed by one statistical molecule of the polyol is 2 or more. When the average number of hydroxyl groups of the polyol is 2 or more, it tends to be possible to further suppress a decrease in the crosslink density of the coating film obtained by curing the one-component coating composition of the present embodiment.

[Fluorine polyol]
As used herein, the term "fluorine polyol" means a polyol containing fluorine in the molecule. Specific examples of the fluorine polyol include fluoroolefins, cyclovinyl ethers, and hydroxys disclosed in JP-A-57-34107 (Reference 1) and JP-A-61-275311 (Reference 2). Examples thereof include copolymers such as alkyl vinyl ether and monocarboxylic acid vinyl ester.

[Polycarbonate polyol]
The polycarbonate polyols are not particularly limited, and examples thereof include those shown in the following (1) to (4).
(1) Dialkyl carbonate such as dimethyl carbonate;
(2) An alkylene carbonate such as ethylene carbonate;
(3) Diaryl carbonate such as diphenyl carbonate;
(4) Obtained by polycondensation of low molecular weight carbonate compounds such as those (1) to (3) above.

[Polyurethane polyol]
The polyurethane polyol is not particularly limited, but can be obtained, for example, by reacting a polyol containing no carboxy group with an isocyanate component by a conventional method.
Examples of the polyol containing no carboxy group include ethylene glycol, propylene glycol and the like as those having a low molecular weight. Further, for example, examples of high molecular weight materials include acrylic polyols, polyester polyols, and polyether polyols.

[Hydroxyl value of polyol]
The hydroxyl value of the polyol per resin is not particularly limited, but is preferably 10 mgKOH / resin g or more and 300 mgKOH / resin g or less.
When the hydroxyl value per resin is at least the above lower limit value, it tends to be possible to suppress the decrease in the crosslink density and more sufficiently achieve the desired physical properties. When the hydroxyl value per resin is not more than the above upper limit value, it is possible to suppress an excessive increase in the crosslink density and to improve the mechanical properties of the coating film obtained by curing the one-component coating composition of the present embodiment. It tends to be improved.
The hydroxyl value of the polyol can be measured according to JIS K1557.

<Other additives>
The resin composition of the present embodiment may further contain other additives.
Other additives include, for example, curing agents that can react with crosslinkable functional groups in polyols, curing catalysts, solvents, pigments (constitution pigments, coloring pigments, metallic pigments, etc.), ultraviolet absorbers, light stabilizers, radicals. Examples thereof include stabilizers, anti-yellowing agents that suppress coloring during the baking process, coating surface adjusting agents, flow adjusting agents, pigment dispersants, defoaming agents, thickeners, and film-forming aids.

Examples of the curing agent include melamine resin, urea resin, epoxy group-containing compound or resin, carboxyl group-containing compound or resin, acid anhydride, alkoxysilane group-containing compound or resin, hydrazide compound and the like.

The curing catalyst may be a basic compound or a Lewis acidic compound.
Examples of the basic compound include metal hydroxides, metal alkoxides, metal carboxylates, metal acetylacetylates, hydroxides of onium salts, onium carboxylates, halides of onium salts, and metal salts of active methylene compounds. Examples thereof include onium salts of active methylene compounds, aminosilanes, amines, phosphines and the like. As the onium salt, an ammonium salt, a phosphonium salt or a sulfonium salt is suitable.
Examples of the Lewis acidic compound include an organic tin compound, an organic zinc compound, an organic titanium compound, and an organic zirconium compound.

Examples of the solvent include those similar to those exemplified in the block polyisocyanate composition.

In addition, pigments (constitution pigments, coloring pigments, metallic pigments, etc.), ultraviolet absorbers, light stabilizers, radical stabilizers, anti-yellowing agents that suppress coloring during the baking process, coating surface conditioners, flow conditioners, pigments As the dispersant, antifoaming agent, thickener and film-forming auxiliary, known ones can be appropriately selected and used.

<Manufacturing method of resin composition>
The resin composition of the present embodiment can be used for both solvent-based and water-based bases. When the resin composition contains the above-mentioned block polyisocyanate composition, a resin composition having excellent low-temperature curability at 80 ° C. or lower when formed into a resin film has not been known so far, and thus is water-based. Is preferably used as a resin composition of.

When producing an aqueous-based resin composition (aqueous resin composition), first, a curing agent capable of reacting with a polyol or an aqueous dispersion thereof or a water-soluble substance with a crosslinkable functional group in the polyol, if necessary. , Curing catalyst, solvent, pigments (constitution pigment, coloring pigment, metallic pigment, etc.), ultraviolet absorber, light stabilizer, radical stabilizer, anti-yellowing agent that suppresses coloring during baking process, coating surface conditioner, flow Add additives such as adjusters, pigment dispersants, defoamers, thickeners, and film-forming aids. Next, the hydrophilic polyisocyanate composition, the blocked polyisocyanate composition, or an aqueous dispersion thereof is added as a curing agent, and if necessary, water or a solvent is further added to adjust the viscosity. Then, the water-based resin composition (water-based resin composition) can be obtained by forcibly stirring with a stirring device.

When producing a solvent-based resin composition, first, a curing agent, a curing catalyst, a solvent, pigments (curing agent, curing catalyst, solvent, pigments) capable of reacting with a crosslinkable functional group in the polyol or a solvent diluted product thereof, if necessary, are added. Constituent pigments, coloring pigments, metallic pigments, etc.), UV absorbers, light stabilizers, radical stabilizers, anti-yellowing agents that suppress coloring during the baking process, coating surface adjusters, flow conditioners, pigment dispersants, defoamers Add additives such as agents, thickeners, and film-forming aids. Next, the hydrophilic polyisocyanate composition or the blocked polyisocyanate composition is added as a curing agent, and if necessary, a solvent is further added to adjust the viscosity. Then, the solvent-based resin composition can be obtained by stirring by hand or using a stirring device such as a magella.

≪Resin film≫
The resin film of the eighth embodiment is formed by curing the resin composition of the seventh embodiment. The resin film of the present embodiment has excellent hardness by using the resin composition containing the hydrophilic polyisocyanate composition of the fifth embodiment. Further, when the resin composition containing the block polyisocyanate composition of the sixth embodiment is used, the curability at a low temperature of about 80 ° C. or lower is further excellent.

The resin film of the present embodiment is cured by coating the above resin composition on a base material using a known method such as roll coating, curtain flow coating, spray coating, bell coating, electrostatic coating, and heating. It can be obtained by.

From the viewpoint of energy saving and heat resistance of the base material, the heating temperature is preferably about 60 ° C. or higher and about 120 ° C. or lower, more preferably about 65 ° C. or higher and about 110 ° C. or lower, and further preferably about 70 ° C. or higher and about 100 ° C. or lower.
From the viewpoint of energy saving and heat resistance of the base material, the heating time is preferably about 1 minute or more and about 60 minutes or less, and more preferably about 2 minutes or more and about 40 minutes or less.

The base material is not particularly limited, and for example, the outer panel of an automobile body such as a passenger car, a truck, a motorcycle, or a bus; an automobile part such as a bumper; an outer panel of a household electric product such as a mobile phone or an audio device. Part; Various films and the like can be mentioned.

The material of the base material is not particularly limited, and is, for example, iron, aluminum, brass, copper, tin, stainless steel, zinc-plated steel, zinc alloy (Zn-Al, Zn-Ni, Zn-Fe, etc.) plating. Metallic materials such as steel; polyethylene resin, polypropylene resin, acrylonitrile-butadiene-styrene (ABS) resin, polyamide resin, acrylic resin, vinylidene chloride resin, polycarbonate resin, polyurethane resin, epoxy resin and other resins, various FRP (fibers) Plastic materials such as reinforced plastics); inorganic materials such as glass, cement and concrete; textile materials such as wood, paper and cloth.

The base material is obtained by subjecting the surface of the metal material or the metal surface of a vehicle body or the like molded from the metal material to a surface treatment such as a phosphate treatment, a chromate treatment, or a composite oxide treatment. In addition, a coating film may be formed on the coating film. As the base material on which the coating film is formed, even if the base material is surface-treated as necessary and the undercoat coating film is formed on the base material, for example, the vehicle body in which the undercoat coating film is formed by the electrodeposition paint. Good. The base material may be a surface of the plastic material or a plastic surface of an automobile part or the like molded from the plastic material, which has been subjected to a desired surface treatment. Further, the base material may be a combination of a plastic material and a metal material.

Hereinafter, the present embodiment will be described in more detail based on Examples and Comparative Examples, but the present embodiment is not limited to the following Examples.

<< Examples 1-1 to 1-18 and Comparative Examples 1-1 to 1-6 >>
<Test items>
The blocked polyisocyanate compositions obtained in Examples and Comparative Examples were measured and evaluated for their physical characteristics according to the methods shown below.

[Physical characteristics 1-1]
(Isocyanate group (NCO) content)
In order to measure the NCO content of polyisocyanate, polyisocyanate before blocking with a blocking agent was used as a measurement sample.

First, 2 g or more and 3 g or less of the measurement sample were precisely weighed in a flask (Wg). Then, 20 mL of toluene was added to dissolve the measurement sample. Then, 20 mL of a toluene solution of 2N-n-butylamine was added, and after mixing, the mixture was allowed to stand at room temperature for 15 minutes. Then 70 mL of isopropyl alcohol was added and mixed. This solution was then titrated into an indicator with a 1N hydrochloric acid solution (Factor F). The obtained titration value was defined as V2 mL. Then, the same operation was carried out without the polyisocyanate sample, and the obtained titration value was set to V1 ml. Next, the isocyanate group (NCO) content (isocyanate group (NCO) content) (mass%) of the polyisocyanate was calculated from the following formula.

Isocyanate group (NCO) content (% by mass) = (V1-V2) x F x 42 / (W x 1000) x 100

[Physical characteristics 1-2]
(Number average molecular weight)
The number average molecular weight is a polystyrene-based number average molecular weight measured by gel permeation chromatography (GPC) using the following apparatus. In order to measure the number average molecular weight of polyisocyanate, polyisocyanate before blocking with a blocking agent was used as a measurement sample. The measurement conditions are shown below.

(Measurement condition)
Equipment: HLC-802A manufactured by Tosoh Corporation
Column: Made by Tosoh Corporation, G1000HXL x 1
G2000HXL x 1
G3000HXL x 1 Carrier: Tetrahydrofuran Detection method: Differential refractometer

[Physical characteristics 1-3]
(Average number of isocyanate functional groups)
For the average number of isocyanate functional groups (average number of NCOs) of polyisocyanate, the average number of isocyanate functional groups was determined by the following formula. In the formula, "Mn" is the number average molecular weight of the polyisocyanate before being blocked by the blocking agent for the blocked polyisocyanate composition, and the value measured in the above "Physical Properties 1-2" was used. The “NCO content” is the isocyanate group content of the polyisocyanate measured before blocking with the blocking agent for the blocked polyisocyanate composition, and the value calculated in the above “Physical Properties 1-1” was used.

Average number of isocyanate functional groups = (Mn x NCO content x 0.01) / 42

[Physical characteristics 1-4]
(Solid content of blocked polyisocyanate composition)
The solid content of the blocked polyisocyanate composition was determined as follows.
First, an aluminum dish having a bottom diameter of 38 mm was precisely weighed. Next, about 1 g of the block polyisocyanate composition produced in Examples and Comparative Examples was placed on an aluminum dish and weighed precisely (W1). The blocked polyisocyanate composition was then adjusted to a uniform thickness. Next, the blocked polyisocyanate composition on an aluminum dish was held in an oven at 105 ° C. for 1 hour. Then, after the aluminum dish reached room temperature, the blocked polyisocyanate composition remaining on the aluminum dish was precisely weighed (W2). Next, the solid content (mass%) of the blocked polyisocyanate composition was calculated from the following formula.

Solid content of block polyisocyanate composition [mass%] = W2 / W1 × 100

[Physical characteristics 1-5]
(Surface tension of dispersant at 25 ° C)
Each dispersant used in Examples and Comparative Examples was diluted with water to prepare a dispersant aqueous solution containing 0.1% by mass of the anionic dispersant and water with respect to the total mass of the aqueous solution. Then, using this dispersant aqueous solution, the surface tension at 25 ° C. was measured by the Wilhelmi method.

[Preparation of resin composition]
Acrylic polyol (Setaqua (registered trademark) 6515 (trade name) manufactured by Nuplex, OH (%) (on solids) = 3.3, Acid value (mgKOH / g) = 9.9, resin content 45%) and each. The block polyisocyanate composition is blended so that the ratio of the molar amount of isocyanate groups to the molar amount of hydroxyl groups (isocyanate group / hydroxyl group) is 1, and ion-exchanged water is further blended to obtain a solid content of 40% by mass. To obtain a resin composition.

[Evaluation 1-1] Storage stability Measure the initial viscosity of 20 g of the obtained resin composition and the viscosity when stored in a 20 mL glass bottle at 40 ° C. for 10 days (Viscometer: RE manufactured by Toki Sangyo Co., Ltd.). -85R). The ratio of the viscosity after storage to the initial viscosity was calculated. When the ratio of the viscosity after storage to the initial viscosity is 2.5 or less and no gelation or precipitation is observed, it is evaluated as good, and the ratio of the viscosity after storage to the initial viscosity is more than 1. A value close to 1 and a value of 1 or less were evaluated as particularly good.

[Evaluation 1-2] Low-temperature curability The obtained resin composition was coated on a polypropylene (PP) plate so as to have a dry film thickness of 40 μm, and then heat-dried at 80 ° C. for 30 minutes to obtain a resin film. The obtained resin film was stored at room temperature (23 ° C.) for 1 week, and the gel fraction was measured. The gel fraction was determined as a percentage (mass%) of the value obtained by dividing the mass of the undissolved portion when the resin film was immersed in acetone at 23 ° C. for 24 hours by the mass before immersion. Those having a gel fraction of 80% by mass or more were evaluated as good.

<Synthesis of polyisocyanate>
[Synthesis Example 1-1]
(Synthesis of polyisocyanate P-1)
A polyester polyol (manufactured by Daicel Chemical Co., Ltd.) derived from HDI: 100 parts by mass and trihydric alcohol and ε-caprolactone in a four-necked flask equipped with a thermometer, a stirring blade and a reflux condenser under a nitrogen stream. , "Praxel 303" (trade name)): 5.1 parts by mass was charged, and the temperature inside the reactor was maintained at 90 ° C. for 1 hour under stirring to carry out a urethanization reaction. After that, the temperature inside the reactor was maintained at 60 ° C., the isocyanurate-forming catalyst tetramethylammonium capriate was added, and when the yield reached 51% by mass, phosphoric acid was added to stop the reaction. After filtering the reaction solution, unreacted HDI was removed using a thin film evaporator to obtain an isocyanurate-type polyisocyanate (hereinafter, may be referred to as "polyisocyanate P-1"). The obtained polyisocyanate P-1 had an NCO content of 18.8% by mass, a number average molecular weight of 1130, and an average number of isocyanate groups of 5.1. ^{In addition, GPC analysis and 1} H-NMR analysis were performed on the obtained polyisocyanate P-1, and it was confirmed that an isocyanurate trimer was present.

[Synthesis Example 1-2]
(Synthesis of polyisocyanate P-2)
HDI: 80 parts by mass, IPDI: 20 parts by mass, and trimeticol propane: 3.4, which is a trivalent alcohol, in a four-necked flask equipped with a thermometer, a stirring blade and a reflux condenser under a nitrogen stream. A mass portion was charged, and the temperature inside the reactor was maintained at 90 ° C. for 1 hour under stirring to carry out a urethanization reaction. After that, the temperature inside the reactor was maintained at 77 ° C., isocyanurate-forming catalyst tetramethylammonium capriate: 0.012 parts by mass was added, and when the yield reached 45% by mass, phosphoric acid was added to stop the reaction. After filtering the reaction solution, unreacted HDI and IPDI were removed using a thin film evaporator to obtain an isocyanurate-type polyisocyanate (hereinafter, may be referred to as "polyisocyanate P-2"). The obtained polyisocyanate P-2 had an NCO content of 19.1% by mass, a number average molecular weight of 1210, and an average number of isocyanate groups of 5.5. ^{In addition, GPC analysis and 1} H-NMR analysis were performed on the obtained polyisocyanate P-2, and it was confirmed that the isocyanurate trimer was present.

<Manufacturing of blocked polyisocyanate composition>
[Example 1-1]
(Production of Block Polyisocyanate Composition BL-a1)
Polyisocyanate P-1: 100 parts by mass, methoxypolyethylene glycol (MPG-081) obtained in Synthesis Example 1-1 in a four-necked flask equipped with a thermometer, stirring blades and a reflux cooling tube under a nitrogen stream. Ethethylene oxide repeating unit: 15 pieces, manufactured by Nippon Emulsifier Co., Ltd.): 24 parts by mass (8 mol% with respect to 100 mol% of isocyanate groups), 2-ethylhexyl acid phosphate (JP-508T, manufactured by Johoku Chemical Industry Co., Ltd.): 0.01 parts by mass and 67 parts by mass of dipropylene glycol dimethyl ether (DPDM) were mixed, and the reaction was carried out at 115 ° C. for 2 hours. The reaction solution was cooled to 40 ° C., di-tert-butyl malonate was added as a blocking agent so as to be 1.1 molar equivalents with respect to the molar amount of isocyanate groups in the reaction product, and sodium methylate (28) was added. Mass%)-containing methanol solution: 1.0 part by mass was added as a solution and stirred. The indoor bath was maintained at 50 ° C. and stirred for 6 hours or more. After confirming that the characteristic absorption of isocyanate groups had disappeared in the infrared spectrum, DPDM was added so as to have a solid content of 60% by mass and stirred, and the mixture was stirred at 40 ° C. It was cooled below. After that, polyoxyethylene polycyclic phenyl ether ammonium sulfate (polyoxyethylene (repetition number n = 10 to 15 of oxyethylene) alkyl (alkyl group carbon number C = 1,8,9)) is further added to the reaction solution as a dispersant. (Mono-penta) ammonium sulfate of styryl-phenyl ether) (surface tension at 25 ° C. 40.3 mM / m) was added so as to be 1.5 parts by mass with respect to 100 parts by mass of the solid content of the blocked polyisocyanate. The mixture was further stirred for 30 minutes to obtain a blocked polyisocyanate composition BL-a1.

[Examples 1-2 to 1-11 and Comparative Examples 1-1 to 1-6]
(Production of Block Polyisocyanate Compositions BL-a2-BL-a11 and BL-b1-BL-b6)
Using the same method as in Example 1-1, block poly was used except that the types of blocking agents, the blending amounts of hydrophilic compounds, and the types and blending amounts of dispersants shown in Tables 1, 2 and 4 were used. The isocyanate compositions BL-a2 to BL-a11 and BL-b1 to BL-b6 were produced.

[Example 1-12]
(Production of Block Polyisocyanate Composition BL-a12)
In a four-necked flask equipped with a thermometer, a stirring blade and a reflux cooling tube, di-tert-butyl malonate was added to the polyisocyanate P-1 obtained in Synthesis Example 1-1 under a nitrogen stream. Add 1.1 molar equivalents to the molar amount of isocyanate groups, add DPDM to a solid content of 60% by mass, and further sodium methylate (28% by mass) -containing methanol solution: 1. 0 parts by mass was added, the indoor bath was maintained at 50 ° C., and the mixture was stirred for 6 hours or more, and it was confirmed in the infrared spectrum that the characteristic absorption of the isocyanate group disappeared. Then, after cooling the reaction solution to 40 ° C. or lower, the polyoxyethylene alkyl ether ammonium sulfate salt (compound represented by the following general formula (II-1); hereinafter may be referred to as “compound (II-1)”). (Surface tension at 25 ° C. of 30.7 mN / m) was added at room temperature to obtain a blocked polyisocyanate composition BL-a12.

R ²¹ -O- (CH ₂ CH ₂ O) ₃₀ -SO ₃ NH ₄ (II-1)

In general formula (II-1), R ²¹ is a tridecylic group.

[Examples 1-13 to 1-14]
(Production of Block Polyisocyanate Compositions BL-a13 to BL-a14)
The block polyisocyanate composition BL was used in the same manner as in Example 1-12 except that the types of blocking agents, the blending amounts of hydrophilic compounds, and the types and blending amounts of dispersants shown in Table 3 were used. -A13 to BL-a14 were produced.

[Examples 1-15-1-16]
(Production of Block Polyisocyanate Compositions BL-a15 to BL-a16)
Two types of blocking agents B-1 and B-2 were used. For Examples 1-15, the blending amounts of B-1 and B-2 were B-1: B-2 = 50 mol%: 50 mol in terms of molar ratio. For Examples 1-16, B-1: B-2 = 20 mol%: 80 mol% was used, and the blending amount of the hydrophilic compound shown in Table 3 and the blending amount of the hydrophilic compound were used. Block polyisocyanate compositions BL-a15 to BL-a16 were produced by using the same method as in Example 1-1 except that the type and amount of the dispersant were used.

[Examples 1-17 to 1-18]
(Production of Block Polyisocyanate Compositions BL-a17 to BL-a18)
Using polyisocyanate P-2, two types of blocking agents B-1 and B-2 were used. For Example 1-17, the blending amounts of B-1 and B-2 were B-1: B in molar ratio. Table 3 shows Example 1-18 using B-1: B-2 = 35 mol%: 65 mol% so that -2 = 50 mol%: 50 mol%. Block polyisocyanate compositions BL-a17 to BL-a18 were produced by using the same method as in Example 1-1 except that the blending amount of the hydrophilic compound and the type and blending amount of the dispersant were used.

In addition, the blocked polyisocyanate compositions obtained in Examples and Comparative Examples were evaluated in various ways using the above methods. The results are shown in Tables 1 to 4 below.

In Tables 1 to 4, the types of blocking agents and dispersants are as shown below.
(Blocking agent)
B-1: Di-tert-butyl malonic acid B-2: Diisopropyl malonic acid

(Dispersant)
D-1: Polyoxyethylene polycyclic phenyl ether ammonium sulfate (polyoxyethylene (repetition number of oxyethylene n = 10 to 15) alkyl (alkyl group carbon number C = 1,8,9) (mono to penta) styryl -Ammonium sulfate salt of phenyl ether) (Surface tension at 25 ° C. 40.3 mN / m)
D-2: Polyoxyethylene polycyclic phenyl ether sodium sulfate (polyoxyethylene (repetition number of oxyethylene n = 10 to 15) alkyl (alkyl group carbon number C = 1,8,9) (mono to penta) Sodium sulfate salt of styryl-phenyl ether) (surface tension at 25 ° C. 41.5 mN / m)

D-3: Polyoxyethylene alkyl ether ammonium sulfate salt (compound represented by the following general formula (II-2); hereinafter may be referred to as "compound (II-2)") (surface tension at 25 ° C. 40. 4mN / m)

R ²² -O- (CH ₂ CH ₂ O) ₈ -SO ₃ NH ₄ (II-2)

In the general formula (II-2), R ²² is an alkyl group having 12 or 13 carbon atoms. Compound (II-2) is a mixture of an alkyl group having 12 carbon atoms and an alkyl group having 13 carbon atoms ^{in R 22.}

D-4: Polyoxyalkylene alkyl ether phosphoric acid ester (compound represented by the following general formula (II-3); hereinafter may be referred to as "compound (II-3)") (surface tension 30 at 25 ° C.) .7mN / m)

R ²³ -O- (CH ₂ CH ₂ O) ₂ -OPOOHONa (II-3)

In the general formula (II-3), R ²³ is a 2-ethylhexyl group.

D-5: Polyoxyethylene alkyl ether sulfate ester salt (compound represented by the following general formula (II-4); hereinafter may be referred to as "compound (II-4)") (surface tension 52 at 25 ° C.) .1mN / m)

R ²⁴ -O- (CH ₂ CH ₂ O) ₆₀ -SO ₃ Na (II-4)

In the general formula (II-4), R ²⁴ is an alkyl group having 12 or 13 carbon atoms. Compound (II-4) is a mixture of an alkyl group having 12 carbon atoms and an alkyl group having 13 carbon atoms ^{in R 24.}

D-6: Polyoxyethylene alkyl ether ammonium sulfate salt (compound (II-1) above) (surface tension at 25 ° C. 38.8 mN / m)

D-7: Polyoxyethylene alkyl ether sodium sulfate (compound represented by the following general formula (II-5); hereinafter may be referred to as "compound (II-5)") (surface tension 45 at 25 ° C.) .9mN / m)

R ²⁵ -O- (CH ₂ CH ₂ O) ₂₀ -SO ₃ Na (II-5)

In the general formula ^{(II-5), R 25} is an alkyl group having 12 or 13 carbon atoms. Compound (II-5) is a mixture of an alkyl group having 12 carbon atoms and an alkyl group having 13 carbon atoms ^{in R 25.}

Further, in Table 4, regarding the storage stability, the ratio of the viscosity after storage to the initial viscosity could not be calculated because gelation or precipitation occurred.

From Tables 1 to 4, the blocked polyisocyanate compositions BL-a1 to BL-a18 containing a dispersant having a surface tension of 38.8 mN / m or more and 45.9 mN / m or less at 25 ° C. (Examples 1-1 to 1-). In 18), the storage stability of the resin composition was good, and the low-temperature curability of the resin film was good.
Further, in the blocked polyisocyanate compositions BL-a1 to BL-a9 (Examples 1-1 to 1-9) in which the content of the hydrophilic compound is different, the lower the blending amount of the hydrophilic compound, the more the resin composition and the resin composition. There was a tendency for the storage stability to be better when it was used.

On the other hand, block polyisocyanate compositions BL-b1 to BL-b6 containing or not containing a dispersant having a surface tension of 30.7 mN / m or 52.1 mN / m at 25 ° C. (Comparative Example 1-). In 1 to 1-6), when the resin composition was prepared, gelation or precipitation occurred, and the storage stability was poor.

<< Examples 2-1 to 2-42 and Comparative Examples 2-1 to 2-12 >>
<Test items>
The physical characteristics of the polyol were measured according to the methods shown below. Regarding the solid content of the blocked polyisocyanate composition and the surface tension of the dispersant at 25 ° C., the same methods as in "Examples 1-1 to 1-18 and Comparative Examples 1-1 to 1-6" were used. The measurement was performed. The resin compositions obtained in Examples and Comparative Examples were evaluated according to the methods shown below. The storage stability and low-temperature curability were evaluated using the same methods as in "Examples 1-1 to 1-18 and Comparative Examples 1-1 to 1-6".

[Physical characteristics 2-1]
(Glass-transition temperature)
The glass transition temperature of the polyol is a condition in which the organic solvent and water in the polyol solution are blown under reduced pressure and then vacuum dried using a differential scanning calorimetry (DSC) measuring device at a heating rate of 5 ° C./min. The value measured in 1 was used as the glass transition temperature.

[Physical characteristics 2-2]
(Weight average molecular weight)
The weight average molecular weight of the polyol is a polystyrene-based weight average molecular weight measured by GPC using the following apparatus. Each polyol used in Examples and Comparative Examples was used as a measurement sample. The measurement conditions are shown below.

(Measurement condition)
Equipment: HLC-802A manufactured by Tosoh Corporation
Column: Made by Tosoh Corporation, G1000HXL x 1
G2000HXL x 1
G3000HXL x 1 Carrier: Tetrahydrofuran Detection method: Differential refractometer

[Physical characteristics 2-3]
(Hydroxy group value)
The hydroxyl value of the polyol was measured and calculated by the potentiometric titration method. The hydroxyl value is a value with respect to the solid content in the polyol.

[Evaluation 2-1]
(Tensile strength)
The obtained resin composition was coated on a polypropylene (PP) plate so as to have a dry film thickness of 40 μm, and then heated and dried at 80 ° C. for 30 minutes to obtain a resin film. The obtained resin film was cut into a width of 10 mm and a length of 40 mm, set so that the distance between chucks was 20 mm, and a tensile test was carried out at a speed of 20 mm / min. The tensile strength was calculated with the maximum point stress at that time as the maximum stress value.

<Synthesis of polyisocyanate>
[Synthesis Example 2-1] Synthesis of Polyisocyanate P-1 Isocyanurate-type polyisocyanate (hereinafter, may be referred to as "polyisocyanate P-1") by using the same method as in the above synthesis example "1-1". ) Was obtained.

<Manufacturing of blocked polyisocyanate composition>
[Example 2-1]
(Production of Block Polyisocyanate Composition BL-a19)
Polyisocyanate P-1: 100 parts by mass obtained in Synthesis Example 2-1 in a four-necked flask equipped with a thermometer, stirring blades and a reflux cooling tube under a nitrogen stream, methoxypolyethylene glycol (MPG-081, Ethethylene oxide repeating unit: 15 pieces, manufactured by Nippon Emulsifier Co., Ltd.): 21 parts by mass (7 mol% with respect to 100 mol% of isocyanate groups), 2-ethylhexyl acid phosphate (JP-508T, manufactured by Johoku Chemical Industry Co., Ltd.): 0.01 parts by mass and 67 parts by mass of dipropylene glycol dimethyl ether (DPDM) were mixed, and the reaction was carried out at 115 ° C. for 2 hours. The reaction solution was cooled to 40 ° C., di-tert-butyl malonate was added as a blocking agent so as to be 1.1 molar equivalents with respect to the molar amount of isocyanate groups in the reaction product, and sodium methylate (28) was added. Mass%)-containing methanol solution: 1.0 part by mass was added as a solution and stirred. The indoor bath was maintained at 50 ° C. and stirred for 6 hours or more. After confirming that the characteristic absorption of isocyanate groups had disappeared in the infrared spectrum, DPDM was added so as to have a solid content of 60% by mass and stirred, and the mixture was stirred at 40 ° C. It was cooled below. After that, polyoxyethylene polycyclic phenyl ether ammonium sulfate (polyoxyethylene (repetition number n = 10 to 15 of oxyethylene) alkyl (alkyl group carbon number C = 1,8,9)) is further added to the reaction solution as a dispersant. (Mono-penta) ammonium sulfate of styryl-phenyl ether) (surface tension at 25 ° C. 40.3 mM / m) was added so as to be 1.3 parts by mass with respect to 100 parts by mass of the solid content of the blocked polyisocyanate. The mixture was further stirred for 30 minutes to obtain a blocked polyisocyanate composition BL-a19.

[Examples 2-2 to 2-11, 2-15 to 2-17 and Comparative Examples 2-1 to 2-6]
(Production of Block Polyisocyanate Compositions BL-a20 to BL-a29, BL-a33 to BL-a35 and BL-b7 to BL-b12)
Using the same method as in Example 2-1 except for the types of blocking agents, the blending amounts of hydrophilic compounds, and the types and blending amounts of dispersants shown in Tables 5 to 8, the blocked polyisocyanate composition was used. The products BL-a20 to BL-a29, BL-a33 to BL-a35 and BL-b7 to BL-b12 were produced.

[Example 2-12]
(Production of Block Polyisocyanate Composition BL-a30)
In a four-necked flask equipped with a thermometer, a stirring blade and a reflux cooling tube, di-tert-butyl malonate was added to the polyisocyanate P-1 obtained in Synthesis Example 2-1 under a nitrogen stream. Add 1.1 molar equivalents to the molar amount of isocyanate groups, add DPDM to a solid content of 60% by mass, and further sodium methylate (28% by mass) -containing methanol solution: 1. 0 parts by mass was added, the indoor bath was maintained at 50 ° C., and the mixture was stirred for 6 hours or more, and it was confirmed in the infrared spectrum that the characteristic absorption of the isocyanate group disappeared. Next, after cooling the reaction solution to 40 ° C. or lower, polyoxyethylene alkyl ether ammonium sulfate (compound (II-1)) (surface tension at 25 ° C., 30.7 mN / m) was added at room temperature to form a blocked polyisocyanate composition. BL-a30 was obtained.

[Examples 2-13 to 2-14]
(Production of Block Polyisocyanate Compositions BL-a31 to BL-a32)
The block polyisocyanate composition BL was used in the same manner as in Example 2-12 except that the types of blocking agents, the blending amounts of hydrophilic compounds, and the types and blending amounts of dispersants shown in Table 6 were used. -A31 to BL-a32 were produced.

In Tables 5 to 8, the types of the blocking agent and the dispersant are the same as those in "Examples 1-1 to 1-18 and Comparative Examples 1-1 to 1-6".

<Manufacturing of polyol>
[Manufacturing Example 2-1]
(Manufacturing of polyol OHP1)
Propylene glycol monomethyl ether: 33 parts by mass was charged into a four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas inlet, and the temperature was raised to 110 ° C. under ventilation of nitrogen gas. After reaching 110 ° C., the aeration of nitrogen gas was stopped, 2-hydroxyethyl methacrylate: 25.1 parts by mass, methyl methacrylate: 40.9 parts by mass, butyl acrylate: 25.7 parts by mass, styrene: 7.0 parts by mass. A mixture consisting of 1.3 parts by mass of acrylic acid and 5.0 parts by mass of 2,2'-azobis (isobutyronitrile): 5.0 parts by mass was added dropwise over 5 hours. Then, after stirring for 3 hours while flowing nitrogen gas at 115 ° C., the mixture was cooled to 60 ° C., propylene glycol monomethyl ether was added, and a solution of polyol OHP1 which is an acrylic polyol resin having a solid content of 60% by mass was obtained. .. Polyols OHP1 has a weight average molecular weight Mw1.21 × 10 ^4, a hydroxyl value of 109mgKOH / g.

[Manufacturing Example 2-2]
(Manufacturing of polyol OHP2)
29 parts by mass of propylene glycol monomethyl ether was charged into a four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas inlet, and the temperature was raised to 110 ° C. under ventilation of nitrogen gas. After reaching 110 ° C., the aeration of nitrogen gas was stopped, 2-hydroxyethyl methacrylate: 22.3 parts by mass, methyl methacrylate: 8.0 parts by mass, butyl acrylate: 26.1 parts by mass, styrene: 42.3 parts by mass. A mixture consisting of parts, acrylic acid: 1.3 parts by mass, and 2,2'-azobis (isobutyronitrile): 2 parts by mass was added dropwise over 5 hours. Then, after stirring for 3 hours while flowing nitrogen gas at 115 ° C., the mixture was cooled to 60 ° C., propylene glycol monomethyl ether was added, and a solution of polyol OHP2, which is an acrylic polyol resin having a solid content of 60% by mass, was obtained. .. Polyols OHP2 has a weight average molecular weight Mw2.62 × 10 ^4, a hydroxyl value of 139mgKOH / g.

[Manufacturing Example 2-3]
(Manufacturing of polyol OHP3)
Propylene glycol monomethyl ether: 25 parts by mass was charged into a four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas inlet, and the temperature was raised to 110 ° C. under ventilation of nitrogen gas. After reaching 110 ° C., the aeration of nitrogen gas was stopped, 2-hydroxyethyl methacrylate: 15.2 parts by mass, 2-ethylhexyl acrylate: 18.0 parts by mass, methyl methacrylate: 58.3 parts by mass, styrene: A mixture consisting of 7.0 parts by mass, acrylic acid: 1.50 parts by mass, and 2,2'-azobis (isobutyronitrile): 1.5 parts by mass was added dropwise over 5 hours. Then, after stirring for 3 hours while flowing nitrogen gas at 115 ° C., the mixture was cooled to 60 ° C., propylene glycol monomethyl ether was added, and a solution of polyol OHP3, which is an acrylic polyol resin having a solid content of 60% by mass, was obtained. .. Polyols OHP3 has a weight average molecular weight Mw3.52 × 10 ^4, a hydroxyl value of 66mgKOH / g.

[Manufacturing Example 2-4]
(Manufacturing of polyol OHP4)
Propylene glycol monomethyl ether: 45 parts by mass was charged into a four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas inlet, and the temperature was raised to 115 ° C. under ventilation of nitrogen gas. After reaching 115 ° C., the aeration of nitrogen gas was stopped, 2-hydroxyethyl methacrylate: 28.2 parts by mass, methyl methacrylate: 31.5 parts by mass, butyl acrylate: 32.0 parts by mass, styrene: 7.0 parts by mass. A mixture consisting of parts, acrylic acid: 1.3 parts by mass, and 2,2'-azobis (isobutyronitrile): 8 parts by mass was added dropwise over 5 hours. Then, after stirring for 3 hours while flowing nitrogen gas at 115 ° C., the mixture was cooled to 60 ° C., propylene glycol monomethyl ether was added, and a solution of polyol OHP4, which is an acrylic polyol resin having a solid content of 60% by mass, was obtained. .. Polyols OHP4 has a weight average molecular weight Mw7.20 × 10 ^3, a hydroxyl value of 150 mgKOH / g.

<Manufacturing of resin composition>
[Examples 2-18 to 2-42 and Comparative Examples 2-7 to 2-12]
(Production of Resin Compositions S-a1 to S-a25 and S-b1 to S-b6)
The solvent was evaporated to 70% by mass of the solid content of each polyol solution by an evaporator, and each block polyisocyanate composition obtained in Example or Comparative Example was added to the molar amount of the isocyanate group with respect to the molar amount of the hydroxyl group. The mixture was blended so that the amount ratio (isocyanate group / hydroxyl group) was 1, and ion-exchanged water was further blended to prepare a solid content of 40% by mass to obtain a resin composition. In the resin compositions S-a21 and S-a22 (Examples 2-38 and 2-39), the blocked polyisocyanate compositions BL-a9 and BL obtained in Examples 1-9 and 1-10. -A10 was used respectively.

In Tables 9 to 13, the types of polyols are as shown below.
(Polyol)
OHP1: Glass transition temperature Tg27.2 ℃, weight average molecular weight Mw1.21 × 10 ^4, a hydroxyl value 109mgKOH / g (as solid content)
OHP2: Glass transition temperature Tg 29.3 ° C., weight average molecular weight Mw 2.62 × 10 ⁴ , hydroxyl value 139 mgKOH / g (as solid content)
OHP3: Glass transition temperature Tg44.5 ℃, weight average molecular weight Mw3.52 × 10 ^4, a hydroxyl value 66mgKOH / g (as solid content)
OHP4: Glass transition temperature Tg 15.2 ° C., weight average molecular weight Mw 7.20 × 10 ³ , hydroxyl value 150 mgKOH / g (as solid content)

The resin compositions obtained in Examples and Comparative Examples were evaluated in various ways using the above methods. The results are shown in Tables 9-13 below. In Tables 9 to 13, the blending amount of the blocked polyisocyanate composition is shown by the solid content (parts by mass) of the blocked polyisocyanate composition with respect to 100 parts by mass of the polyol. In Table 13, regarding the storage stability, the ratio of the viscosity after storage to the initial viscosity could not be calculated because gelation or precipitation occurred.

From Tables 9 to 13, the resin compositions S-a1 to S-a25 (Examples 2-18 to 2-42) have good storage stability, and have low-temperature curability and tension when formed into a resin film. The strength was good.
Further, comparison of resin compositions S-a4-S-a6 and S-a15-S-a17 (Examples 2-21 to 2-23 and 2-32 to 2-34) in which the types of polyols are different, and In comparison of the resin compositions S-a8 to S-a9 and S-a23 to S-a24 (Examples 2-25 to 2-27 and 2-40 to 2-42), the glass transition temperature Tg of the polyol was lowered. Moreover, as the weight average molecular weight decreases, the storage stability tends to be better, while as the glass transition temperature Tg of the polyol increases and the weight average molecular weight increases, the resin film and the resin film are formed. There was a tendency for the low temperature curability and tensile strength to be better.

On the other hand, in the resin compositions S-b1 to S-b6 (Comparative Examples 2-7 to 2-12), gelation or precipitation occurred when the resin composition was used, and the storage stability was poor. ..

(Blocking agent)
B-3: 1,2,3-triazole B-4: 1,2,4-triazole

(solvent)
DMF: N, N-dimethylformamide

(Carboxylate)
C: Potassium acetate

(Urethane catalyst)
LH-10: An aqueous emulsion containing 10% by mass of dibutyltin dilaurate (DBTDL) with respect to the total mass of the emulsion (Borchers, "LH-10" (trade name)).

[Physical characteristics 3-1]
Effective NCO content [mass%]
= [(Solid content of blocked polyisocyanate composition [mass%]) x {(mass of polyisocyanate used in blocking reaction) x NCO%}] / (mass of blocked polyisocyanate composition after blocking reaction)

[Physical characteristics 3-2]
(Content of counter cation of carboxylate)
The content of the counter cation of the carboxylate contained in the blocked polyisocyanate composition was measured by the following method.
First, ultrapure water was added to the sample, mixed, and allowed to stand for several hours. Then, the aqueous layer was filtered with a filter and then measured by an ion chromatograph to obtain the counter cation content of the carboxylate. The measurement conditions are as shown below.

(Measurement condition)
Equipment: Shimadzu Ion Chromatograph Column: Sim-pack-IC-C4
4.6mm I. D. × 150 mmL, 7 μm (manufactured by SHIMADZU)
Mobile phase: A) 3.5 mmol / L Oxalic Acid
B) 1 mmol / L 18-crown-6
Flow velocity: 1.0 mL / min Sample concentration: 1.0 mass%
Injection volume: 50 μL
Temperature: 45 ° C
Detection: CDD

[Manufacturing Example 3-1]
<Manufacturing of blocked polyisocyanate composition>
(Production of Block Polyisocyanate Composition BL-a36)
The inside of the four-necked flask equipped with the stirrer, thermometer, reflux cooling tube, and nitrogen blowing tube was made into a nitrogen atmosphere, and the polyisocyanate P-1 obtained in the above [Synthesis Example 1-1] was added to 100 parts by mass. , Methoxypolyethylene glycol (MPG-081, ethylene oxide repeating unit: 15, manufactured by Nippon Emulsifier Co., Ltd.): 15.0 parts by mass (5 mol% with respect to NCO% of polyisocyanate P-1), and heated to 120 ° C. It was held for 2 hours with heating and stirring. Next, the reaction solution was cooled to about 80 ° C. or higher and 110 ° C. or lower, 1,2,3-triazole: 30.8 parts by mass was gradually added, and under temperature conditions of 80 ° C. or higher and lower than 120 ° C. for 1 hour or longer. The reaction was carried out with stirring for about 4 hours or less. Then, the FT-IR spectrum was measured and it was confirmed that the isocyanate group was blocked. Further, N, N-dimethylformamide was added to the reaction solution so that the solid content became 60%, and the mixture was stirred at 60 ° C. until uniform. Subsequently, the mixture was cooled to 30 ° C., and the above D-1 (polyoxyethylene polycyclic phenyl ether ammonium sulfate salt (polyoxyethylene (repetition number n = 10 to 15 of oxyethylene) alkyl (alkyl group)) was added to the reaction solution as a dispersant. Carbon number C = 1,8,9) (mono-penta) ammonium sulfate of styryl-phenyl ether) (surface tension at 25 ° C. 40.3 mM / m)) was 1 with respect to 100 parts by mass of solid content of blocked polyisocyanate. The mixture was added so as to have a volume of .5 parts by mass, and the mixture was further stirred for 30 minutes to obtain a blocked polyisocyanate composition BL-a36.

[Manufacturing Example 3-2]
<Manufacturing of blocked polyisocyanate composition>
(Production of Block Polyisocyanate Composition BL-a37)
As the dispersant, the D-2 (polyoxyethylene polycyclic phenyl ether sodium sulfate sodium salt (polyoxyethylene (repetition number n = 10 to 15 of oxyethylene) alkyl (alkyl group carbon number C = 1,8,9)) Block polyisocyanate composition BL-a37 in the same manner as in Production Example 3-1 except that (mono-penta) sodium sulfate of styryl-phenyl ether) (surface tension at 25 ° C. 41.5 mN / m) was used. Got

[Manufacturing Example 3-3]
<Manufacturing of blocked polyisocyanate composition>
(Production of Block Polyisocyanate Composition BL-a38)
The same as in Production Example 3-1 except that D-3 (polyoxyethylene alkyl ether ammonium sulfate (compound (II-2)) (surface tension at 25 ° C. 40.4 mN / m)) was used as the dispersant. A block polyisocyanate composition BL-a38 was obtained.

[Manufacturing Example 3-4]
(Production of Block Polyisocyanate Composition BL-a39)
The inside of the four-necked flask equipped with the stirrer, thermometer, reflux cooling tube, and nitrogen blowing tube was made into a nitrogen atmosphere, and the polyisocyanate P-1 obtained in the above [Synthesis Example 1-1]: 100 parts by mass, and A 15.0 parts by mass of methoxypolyethylene glycol (MPG-081, ethylene oxide repeating unit: 15, manufactured by Nippon Emulsifier Co., Ltd.) was charged and held at 120 ° C. for 2 hours with heating and stirring. Next, the reaction solution was cooled to about 80 ° C. or higher and 110 ° C. or lower, 1,2,4-triazole: 30.8 parts by mass was gradually added, and the temperature condition was 80 ° C. or higher and lower than 120 ° C. for 1 hour or longer. The reaction was carried out with stirring for about 4 hours or less. Then, the FT-IR spectrum was measured and it was confirmed that the isocyanate group was blocked. Further, N, N-dimethylformamide was added to the reaction solution so that the solid content was 60% by mass, stirred at 60 ° C. until uniform, and then cooled to 30 ° C. as a dispersant in the reaction solution. D-1 (Polyoxyethylene polycyclic phenyl ether ammonium sulfate salt (polyoxyethylene (repetition number of oxyethylene n = 10 to 15) alkyl (alkyl group carbon number C = 1,8,9) (mono to penta) Styryl-phenyl ether ammonium sulfate salt) (surface tension at 25 ° C. 40.3 mM / m)) was added so as to be 1.5 parts by mass with respect to 100 parts by mass of the solid content of the blocked polyisocyanate, and further stirred for 30 minutes. Then, a blocked polyisocyanate composition BL-a39 was obtained.

[Manufacturing Example 3-5]
<Manufacturing of blocked polyisocyanate composition>
(Production of Block Polyisocyanate Composition BL-a40)
As the dispersant, the D-2 (polyoxyethylene polycyclic phenyl ether sodium sulfate sodium salt (polyoxyethylene (repetition number n = 10 to 15 of oxyethylene) alkyl (alkyl group carbon number C = 1,8,9)) Block polyisocyanate composition BL-a40 in the same manner as in Production Example 3-4 except that (mono-penta) sodium sulfate of styryl-phenyl ether) (surface tension at 25 ° C. 41.5 mN / m) was used. Got

[Manufacturing Example 3-6]
<Manufacturing of blocked polyisocyanate composition>
(Production of Block Polyisocyanate Composition BL-a41)
The same as in Production Example 3-4 except that D-3 (polyoxyethylene alkyl ether ammonium sulfate (compound (II-2)) (surface tension at 25 ° C. 40.4 mN / m)) was used as the dispersant. A block polyisocyanate composition BL-a41 was obtained.

[Manufacturing Example 3-7]
<Manufacturing of blocked polyisocyanate composition>
(Production of Block Polyisocyanate Composition BL-a42)
The block polyisocyanate composition BL-a42 was added in the same manner as in Production Example 3-6 except that the dispersant D-3 was added so as to be 0.5 parts by mass with respect to 100 parts by mass of the solid content of the block polyisocyanate. Got

<Preparation of resin composition>
[Example 3-1]
Aqueous acrylic polyol (Setaqua (registered trademark) 6515 (trade name) manufactured by Nuplex, OH (%) (on solids) = 3.3, Acid value (mgKOH / g) = 9.9, resin content 45%): 10 .0 parts by mass (solution weight) and blocked polyisocyanate BL-a36: 4.08 parts by mass (solution weight) (ratio of molar amount of isocyanate groups to molar amount of hydroxyl groups (isocyanate group / hydroxyl group) is 0.80 (To be). Next, potassium acetate: 0.14 parts by mass (0.80% by mass with respect to the total resin solid content weight) and 10% by mass of dibutyltin dilaurate (DBTDL, manufactured by Borchers, "LH-10" (trade name)). )): After adding 0.14 parts by mass (solution weight, 0.80% by mass with respect to the total resin solid content weight) and further adding ion-exchanged water to prepare the solid content to 40% by mass. A small amount of dimethylaminoethanol was added to adjust the pH to 8.0-8.5, and the mixture was stirred at 1000 rpm for 15 minutes using a homodisper to obtain a resin composition.

[Examples 3-2-3-7]
Each block polyisocyanate BL-a37 to 42 is blended so that the ratio of the molar amount of isocyanate groups to the molar amount of hydroxyl groups (isocyanate group / hydroxyl group) is 0.80, and potassium acetate is added to the total resin solid content weight. The same as in Example 3-1 except that the mixture was blended so as to be 0.80% by mass and 10% by mass of dibutyltin dilaurate was added so as to be 0.80% by mass based on the total resin solid content weight. To obtain a resin composition.

[Evaluation 3-1] Storage stability Measure the initial viscosity of 20 g of the obtained resin composition and the viscosity when stored in a 20 mL glass bottle at 40 ° C. for 10 days (Viscometer: RE manufactured by Toki Sangyo Co., Ltd.). -85R). The ratio of the viscosity after storage to the initial viscosity was calculated. When the ratio of the viscosity after storage to the initial viscosity is 2.5 or less and no gelation or precipitation is observed, it is evaluated as good, and the ratio of the viscosity after storage to the initial viscosity is more than 1. A value close to 1 and a value of 1 or less were evaluated as particularly good.

[Evaluation 3-2] Low-temperature curability The obtained resin composition was coated on a polypropylene (PP) plate so as to have a dry film thickness of 40 μm, and then heat-dried at 90 ° C. for 30 minutes to obtain a resin film. The obtained resin film was stored at room temperature (23 ° C.) for 1 week, and the gel fraction was measured. The gel fraction was determined as a percentage (mass%) of the value obtained by dividing the mass of the undissolved portion when the resin film was immersed in acetone at 23 ° C. for 24 hours by the mass before immersion. Those having a gel fraction of 80% by mass or more were evaluated as good.

<Measurement method of physical properties>
[Physical characteristics 4-1]
(Degeneration rate)
Using the hydrophilic polyisocyanate composition as a sample, the ratio of the isocyanate groups modified by the hydrophilic compound to the total molar amount of the isocyanate groups of the alicyclic polyisocyanate was measured by the following method. The ratio can also be said to be the ratio (modification rate) of the isocyanate group modified by the hydrophilic compound to 100 mol% of the isocyanate group of the raw material polyisocyanate. Specifically, unmodified IPDI-based isocyanurate-type polyisocyanate, 1-modified IPDI-based isocyanurate-type polyisocyanate, 2-modified IPDI-based isocyanurate-type polyisocyanate, and 3 at 220 nm of liquid chromatography (LC). It was determined from the peak area ratio of the modified IPDI-based isocyanurate-type polyisocyanate. The equipment and measurement conditions used are as follows.

(Device and measurement conditions)
LC device: Waters, UPLC (trade name)
Column: ACQUITY UPLC HSS T3 1.8 μm manufactured by Waters
C18, inner diameter 2.1 mm x length 50 mm
Flow velocity: 0.3 mL / min
Mobile phase: A = 10 mM ammonium acetate aqueous solution, B = acetonitrile Granant Condition: The initial mobile phase composition is A / B = 98/2, the ratio of B is linearly increased after sample injection, and A / after 10 minutes. B = 0/100.
Detection method: photodiode array detector, measurement wavelength 220 nm

[Physical characteristics 4-2]
(Amount of solid content)
As a sample, a hydrophilic polyisocyanate composition or a blocked polyisocyanate composition was used.
First, an aluminum dish having a bottom diameter of 38 mm was precisely weighed. Next, the sample was precisely weighed on an aluminum plate with about 1 g of the sample placed (W1). The sample was then adjusted to a uniform thickness. Next, the sample on the aluminum plate was held in an oven at 105 ° C. for 1 hour. Then, after the aluminum plate reached room temperature, the sample remaining on the aluminum plate was precisely weighed (W2). Next, the solid content (mass%) of the sample was calculated from the following formula.

Solid content (mass%) = W2 / W1 x 100

[Physical characteristics 4-3]
(Isocyanate group content (NCO%))
Using the raw material polyisocyanate and hydrophilic polyisocyanate composition as samples, the isocyanate group content was measured according to the method described in JIS K7301-1995 (Torrange isocyanate type prepolymer test method for thermosetting urethane elastomer). did. A more specific method for measuring the isocyanate group content is shown below.

(1) 1 g (Wg) of a sample was collected in a 200 mL Erlenmeyer flask, and 20 mL of toluene was added to the flask to dissolve the sample.
(2) After that, 20 mL of a 2.0 N di-n-butylamine-toluene solution was added to the flask, and the flask was allowed to stand for 15 minutes.
(3) 70 mL of 2-propanol was added to the flask and dissolved to obtain a solution.
(4) The solution obtained in (3) above was titrated with 1 mol / L hydrochloric acid to determine a sample titer (V1 mL).
(5) Even when no sample was added, the measurement was carried out in the same manner as in (1) to (3) above, and a blank titration amount (V0 mL) was determined.
The isocyanate group content (NCO%) was calculated from the sample titration and blank titration obtained above using the formula shown below.

[Isocyanate group content] (% by mass) = (V0-V1) x 42 / [W (1g) x 1000] x 100

[Physical characteristics 4-4]
(Number average molecular weight (Mn) and weight average molecular weight (Mw))
The number average molecular weight (Mn) of the raw material polyisocyanate and the weight average molecular weight (Mw) of the hydrophilic polyisocyanate composition are measured by GPC measurement under the measurement conditions shown below to measure the polystyrene-based number average molecular weight and weight average molecular weight. I got it.

(Measurement condition)
Equipment: Tosoh Corporation HLC-8120GPC (trade name)
Column: Tosoh Corporation TSKgel SuperH1000 (trade name) x 1 TSKgel SuperH2000 (trade name) x 1 TSKgel SuperH3000 (trade name) x 1 Carrier: Tetrahydrofuran Detection method: Differential refractometer

[Physical characteristics 4-5]
(Average number of functional groups of isocyanate groups (average number of NCOs))
The average number of functional groups (average number of NCOs) of the isocyanate groups of the polyisocyanate before hydrophilization (before modification with the hydrophilic compound), that is, the raw material polyisocyanate, was calculated by the following formula. In the formula, "Mn" is the number average molecular weight of the raw material polyisocyanate, and the value measured in the above "physical properties 4-4" was used. “NCO%” is the isocyanate group content of the raw material polyisocyanate, and the value calculated in the above “Physical characteristics 4-3” was used.

[Average number of NCOs] = (Mn x [NCO%] x 0.01) / 42

<Evaluation method>
[Evaluation 4-1]
(Water dispersibility)
Ion-exchanged water was added to the hydrophilic polyisocyanate composition or the blocked polyisocyanate composition so that the solid content was 40% by mass with respect to the total mass of the aqueous dispersion, and the disper stirrer was used at a rotation speed of 1000 rpm. After stirring for minutes, defoaming was performed to obtain an aqueous dispersion. The water dispersibility of the obtained aqueous dispersion was evaluated according to the following evaluation criteria.

(Evaluation criteria)
A: It is a liquid state with no precipitate or lumps that can be visually confirmed.
B: It is a liquid state in which there is no precipitate and lumps that can be visually confirmed are partially confirmed.
C: A liquid state in which the precipitate is thinly precipitated and some lumps that can be visually confirmed are confirmed.
D: A liquid state in which a large amount of lumps that can be clearly confirmed and settled or visually confirmed can be confirmed.

[Manufacturing of resin composition]
Acrylic dispersion (manufactured by Allnex, "SETAQUA6515" (trade name), hydroxyl group concentration 3.3 mol% (resin standard), solid content 45% by mass based on the total mass of the acrylic dispersion) and a hydrophilic polyisocyanate composition or The blocked polyisocyanate composition was blended so that the ratio of the molar amount of isocyanate groups to the molar amount of hydroxyl groups (isocyanate group / hydroxyl group) was 1. Further, ion-exchanged water was added to prepare the solid content so as to be 40% by mass with respect to the total mass of the resin composition, and the mixture was stirred with a disper stirrer at a rotation speed of 1000 rpm for 10 minutes to obtain a resin composition. It was.

[Evaluation 4-2]
(König hardness)
The obtained resin composition was coated on a glass plate so as to have a dry film thickness of 40 μm, and then heat-dried at 80 ° C. for 30 minutes to obtain a resin film. The König hardness (times) of the obtained resin film was measured with a König hardness tester.

[Evaluation 4-3]
(Low temperature curability)
Using the same method as in "Evaluation 4-2" above, a polypropylene (PP) plate was coated with a dry film thickness of 40 μm, and then heated and dried at 80 ° C. for 30 minutes to obtain a resin film. The obtained resin film was stored at room temperature (23 ° C.) for 1 week, and then the gel fraction was measured. The gel fraction was determined as a percentage (mass%) of the value obtained by dividing the mass of the undissolved portion when the resin film was immersed in acetone at 23 ° C. for 24 hours by the mass before immersion. Those having a gel fraction of 75% by mass or more were evaluated as good.

<Manufacturing of hydrophilic polyisocyanate composition>
[Example 4-1]
(Production of Hydrophilic Polyisocyanate Composition P-a1)
Isophorone diisocyanate having an isocyanurate group having a solid content of 100% by mass and an isocyanate group content of 17.4% by mass in a four-necked flask equipped with a thermometer, a stirring blade and a reflux cooling tube under a nitrogen stream. Base polyisocyanate (hereinafter sometimes abbreviated as "IPDI-based isocyanurate type PI"): 100 parts by mass, methoxypolyethylene glycol ("MPG-081" (trade name), ethylene oxide repeating unit: 15 pieces, Japan (Manufactured by Emulsifier Co., Ltd.): 8.3 parts by mass (amount of ethylene oxide of 3 mol% with respect to 100 mol% of isocyanate groups) and dipropylene glycol dimethyl ether (DPDM) are mixed and reacted at 115 ° C. for 2 hours. Was done. Then, the reaction solution was cooled to 40 ° C. to obtain a hydrophilic polyisocyanate composition P-a1 having a solid content of 60.1% by mass.

[Examples 4-2 to 4-6 and Comparative Examples 4-1 to 4-4]
(Production of Hydrophilic Polyisocyanate Compositions P-a2-P-a6 and P-b1-P-b4)
Example 4-1 except that the hydrophilic compound methoxypolyethylene glycol MPG-081 was blended so that the molar amount (denaturation rate) of ethylene oxide with respect to 100 mol% of isocyanate groups would be the values shown in Tables 1 and 2. Each hydrophilic polyisocyanate composition was obtained by the same method as in the above.

The physical properties of each of the hydrophilic polyisocyanate compositions obtained in Examples and Comparative Examples were measured using the above method, and various evaluations were performed. The results are shown in Tables 15 and 16.

From Tables 15 to 16, the hydrophilic polyisocyanate compositions P-a1 to P-a6 (Examples 4-1 to 4-6) having a modification rate of 3 mol% or more and 15 mol% or less have good water dispersibility. , The König hardness when made into a resin film was excellent.
Further, in the compositions P-a2 to P-a5 (Examples 4-2 to 4-5) having a denaturation rate of 5 mol% or more and 12 mol% or less, the water dispersibility was particularly good.

On the other hand, in the hydrophilic polyisocyanate compositions P-b1 to P-b4 (Comparative Examples 4-1 to 4-4) having a modification rate of less than 2 mol% or more than 15 mol%, the water-dispersible and resin film was used. All König hardnesses were poor.

<Manufacturing of blocked polyisocyanate composition>
[Example 4-7]
(Production of Block Polyisocyanate Composition BP-a1)
With respect to the hydrophilic polyisocyanate composition P-a1 obtained in Example 4-1 so that the amount of diisopropyl malonate (B-2) as a blocking agent is 1.1 molar equivalents with respect to the molar amount of isocyanate groups. In addition, a methanol solution containing 28% by mass of sodium methylate with respect to the total mass of the solution: 1.0 part by mass (amount as a solution) is added to obtain DPDM having a solid content of 60% by mass. And stirred. The indoor bath was maintained at 55 ° C. and the mixture was stirred for 6 hours or more, and it was confirmed in the infrared spectrum that the characteristic absorption of the isocyanate group disappeared. Then, a block polyisocyanate composition BP-a1 having a solid content of 60.1% by mass was obtained.

[Examples 4-8 to 4-12 and Comparative Examples 4-5 to 4-8]
(Production of Block Polyisocyanate Compositions BP-a2-BP-a6 and BP-b1-BP-b8)
Each block poly was used in the same manner as in Example 4-7, except that the hydrophilic polyisocyanate compositions and blocking agents shown in Tables 17 and 18 were used instead of the hydrophilic polyisocyanate composition P-a1. An isocyanate composition was obtained.

[Example 4-13]
(Production of Block Polyisocyanate Composition BP-a7)
To the hydrophilic polyisocyanate composition P-a2 obtained in Example 4-2, 1.1 mol of di-tert-butyl malonate (B-1) as a blocking agent was added to the molar amount of the isocyanate group. Add the equivalent amount, and add 1.0 part by mass (amount as a solution) of a methanol solution containing 28% by mass of sodium methylate with respect to the total mass of the solution, and add DPDM with a solid content of 60. It was added to a mass% and stirred. The indoor bath was maintained at 55 ° C. and the mixture was stirred for 6 hours or more, and it was confirmed in the infrared spectrum that the characteristic absorption of the isocyanate group disappeared. Then, a block polyisocyanate composition BP-a7 having a solid content of 60.1% by mass was obtained.

[Example 4-14]
(Production of Block Polyisocyanate Composition BP-a8)
Example 4-except that the hydrophilic polyisocyanate composition P-a3 obtained in Example 4-3 was used instead of the hydrophilic polyisocyanate composition P-a2 obtained in Example 4-2. The blocked polyisocyanate composition BP-a8 was obtained by the same method as in 13.

The physical properties of each of the blocked polyisocyanate compositions obtained in Examples and Comparative Examples were measured using the above method, and various evaluations were performed. The results are shown in Tables 17 and 18.

From Tables 17 and 18, in the blocked polyisocyanate compositions BP-a1 to BP-a8 (Examples 4-7 to 4-14) using the hydrophilic polyisocyanate composition having a modification rate of 3 mol% or more and 15 mol% or less. The water dispersibility was good, and the König hardness and low-temperature curability when made into a resin film were excellent.
Further, as the modification rate of the hydrophilic polyisocyanate composition used increased, the water dispersibility and the low-temperature curability when formed into a resin film tended to become better. On the other hand, as the modification rate of the hydrophilic polyisocyanate composition used decreased, the König hardness of the resin film tended to become better.
Further, the blocked polyisocyanate compositions BP-a7 and BP-a8 (Examples 4-13 and 4-14) using di-tert-butyl malonic acid as a blocking agent are blocked using diisopropyl malonic acid as a blocking agent. Compared with the polyisocyanate compositions BP-a2 and BP-a3 (Examples 4-8 and 4-9), the König hardness and low-temperature curability when made into a resin film were more excellent.

On the other hand, in the blocked polyisocyanate compositions BP-b1 to BP-b4 (Comparative Examples 4-5 to 4-8) using the hydrophilic polyisocyanate composition having a denaturation rate of less than 2 mol% or more than 15 mol%, water dispersion was performed. The properties, as well as the hardness and low-temperature curability of the resin film, were all poor.

[Example 4-15]
(Synthesis of polyisocyanate P-c1)
A polyester polyol (manufactured by Daicel Chemical Co., Ltd.) derived from HDI: 100 parts by mass and trihydric alcohol and ε-caprolactone in a four-necked flask equipped with a thermometer, a stirring blade and a reflux condenser under a nitrogen stream. , "Praxel 303" (trade name)): 5.2 parts by mass was charged, and the temperature inside the reactor was maintained at 90 ° C. for 1 hour under stirring to carry out a urethanization reaction. After that, the temperature inside the reactor was maintained at 60 ° C., the isocyanurate-forming catalyst tetramethylammonium capriate was added, and when the yield reached 51% by mass, phosphoric acid was added to stop the reaction. After filtering the reaction solution, unreacted HDI was removed using a thin film evaporator to obtain an isocyanurate-type polyisocyanate (hereinafter, may be referred to as "polyisocyanate P-c1").
The obtained polyisocyanate P-c1 had an NCO content of 18.7% by mass, a number average molecular weight of 1140, and an average number of isocyanate groups of 5.1. In addition, GPC analysis and ¹ H-NMR analysis were performed on the obtained polyisocyanate P-c1 to confirm the presence of isocyanurate trimer.

[Example 4-16]
(Production of Block Polyisocyanate Composition BP-c1)
In a four-necked flask equipped with a thermometer, a stirring blade and a reflux cooling tube, under a nitrogen stream, the polyisocyanate P-c obtained in Example 4-15 by 1: 100 parts by mass, methoxypolyethylene glycol ( MPG-081, ethylene oxide repeating unit: 15, manufactured by Nippon Emulsifier Co., Ltd.): 1.5 parts by mass (0.5 mol% with respect to 100 mol% of isocyanate groups), 2-ethylhexyl acid phosphate (JP-508T, Johoku Chemical Industry Co., Ltd.): 0.01 parts by mass and dipropylene glycol dimethyl ether (DPDM) were prepared so as to have a solid content concentration of 65% by mass, and the reaction was carried out at 115 ° C. for 2 hours. The reaction solution was cooled to 40 ° C., di-tert-butyl malonate was added as a blocking agent so as to be 1.1 molar equivalents with respect to the molar amount of isocyanate groups in the reaction product, and sodium methylate (28) was added. Mass%)-containing methanol solution: 1.0 part by mass was added as a solution, and the mixture was stirred. The indoor bath was maintained at 48 ° C. and stirred for 6 hours or more. After confirming in the infrared spectrum that the characteristic absorption of isocyanate groups had disappeared, DPDM was added so as to have a solid content of 60% by mass and stirred, and the mixture was stirred at 40 ° C. The mixture was cooled below to obtain a blocked polyisocyanate composition BP-c1.

[Example 4-17]
(Production of Block Polyisocyanate Composition BP-d1)
The block polyisocyanate composition BP-c1 and BP-a7 were blended in a four-necked flask equipped with a thermometer, a stirring blade and a reflux condenser under a nitrogen stream at a NCO molar ratio of 95: 5. The mixture was stirred for 30 minutes to obtain a blocked polyisocyanate composition BP-d1 having a solid content of 60.1% by mass.

[Examples 4-18 to 4-20]
In Example 4-18-4-20, a blocked polyisocyanate composition was prepared in the same manner as in Example 4-17 according to Table 19.
The physical properties of each of the obtained blocked polyisocyanate compositions were measured using the above method, and various evaluations were performed. The results are shown in Table 19.

According to the blocked polyisocyanate composition of the present embodiment, it is possible to provide a resin composition having good storage stability. Further, since a resin film having good curability at a low temperature of about 80 ° C. can be formed, it is suitably used for coating a material having low heat resistance.
Further, according to the hydrophilic polyisocyanate composition of the present embodiment, it is possible to provide a resin film having good water dispersibility and excellent hardness.

Claims (35)

Blocked polyisocyanates derived from polyisocyanates and one or more blocking agents,
Anionic dispersant and
A blocked polyisocyanate composition containing
The blocking agent is (A) a compound represented by the following general formula (I),
Or (B) a compound having a heterocycle containing one or more nitrogens,
Including
The anionic dispersant has a surface tension of 0.1% by mass based on the total mass of the aqueous solution measured by the Wilhelmi method at 25 ° C. of the aqueous solution consisting of the anionic dispersant and water of 32 mN /. M or more and 51 mN / m or less,
A blocked polyisocyanate composition, wherein the blocking agent further comprises a carboxylic acid salt when the blocking agent contains a compound having a heterocycle containing one or more of the nitrogen (B).

(In the general formula (I), R ¹¹ is a hydroxy group; an alkyl group which may contain one or more substituents selected from the group consisting of a hydroxy group and an amino group; and a group consisting of a hydroxy group and an alkyl group. Amino group which may contain one or more substituents selected; aryl group which may contain one or more substituents selected from the group consisting of hydroxy group and amino group; or which consists of hydroxy group and amino group It is an alkoxy group that may contain one or more substituents selected from the group. However, the amino group may be formed by connecting two of the substituents to each other to form a ring.
R ¹² , R ¹³ and R ¹⁴ each independently consist of a hydrogen atom; an alkyl group which may contain one or more substituents selected from the group consisting of a hydroxy group and an amino group; or a hydroxy group and an amino group. It is an aryl group that may contain one or more substituents selected from the group. The amino group may be formed by connecting the two substituents to each other to form a ring. However, ^{two or more of R 12} , R ¹³ and R ¹⁴ are not hydrogen atoms. ) Blocked polyisocyanates derived from polyisocyanates and one or more blocking agents,
Anionic dispersant and
A blocked polyisocyanate composition containing
The blocking agent contains a compound represented by the following general formula (I).
The anionic dispersant has a surface tension at 25 ° C. of 32 mN /% of the aqueous solution composed of the anionic dispersant and water, which is 0.1% by mass based on the total mass of the aqueous solution, as measured by the Wilhelmi method. A blocked polyisocyanate composition having a mass of m or more and 51 mN / m or less.

(In the general formula (I), R ¹¹ is a hydroxy group; an alkyl group which may contain one or more substituents selected from the group consisting of a hydroxy group and an amino group; and a group consisting of a hydroxy group and an alkyl group. Amino group which may contain one or more substituents selected; aryl group which may contain one or more substituents selected from the group consisting of hydroxy group and amino group; or which consists of hydroxy group and amino group It is an alkoxy group that may contain one or more substituents selected from the group. However, the amino group may be formed by connecting two of the substituents to each other to form a ring.
R ¹² , R ¹³ and R ¹⁴ each independently consist of a hydrogen atom; an alkyl group which may contain one or more substituents selected from the group consisting of a hydroxy group and an amino group; or a hydroxy group and an amino group. It is an aryl group that may contain one or more substituents selected from the group. The amino group may be formed by connecting the two substituents to each other to form a ring. However, ^{two or more of R 12} , R ¹³ and R ¹⁴ are not hydrogen atoms. ) The blocked polyisocyanate composition according to claim 1 or 2, wherein a part or all of the blocked polyisocyanate has a structural unit derived from a hydrophilic compound. The blocked polyisocyanate composition according to claim 3, wherein the structural unit derived from the hydrophilic compound contains at least one hydrophilic group selected from the group consisting of a nonionic hydrophilic group and an anionic hydrophilic group. .. The blocking agent is represented by the general formula (I) ^{, wherein R 11} is an alkoxy group, R ¹² is a hydrogen group or an alkyl group, and R ¹³ and R ^{14 are alkyl groups.} The blocked polyisocyanate composition according to any one of claims 1 to 4, which comprises one or more compounds. The blocked polyisocyanate according to any one of claims 1 to 5, wherein the content of the anionic dispersant is 0.01 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the blocked polyisocyanate. Composition. The blocked polyisocyanate composition according to any one of claims 1 to 6, wherein the blocked polyisocyanate contains a blocked isocyanurate trimer. The blocked polyisocyanate composition according to any one of claims 1 to 7, wherein the polyisocyanate has an average number of isocyanate functional groups of 2.0 or more. The blocked polyisocyanate according to any one of claims 1 to 8, wherein the polyisocyanate is a polyisocyanate derived from one or more kinds of diisocyanates selected from the group consisting of an aliphatic diisocyanate and an alicyclic diisocyanate. Composition. The blocked polyisocyanate composition according to claim 1, wherein the blocking agent comprises a compound having a heterocycle containing one or more of the nitrogen (B). The blocked polyisocyanate composition according to claim 10, wherein the content of the counter cation of the carboxylate is 0.1% by mass or more and 20% by mass or less with respect to the total mass of the blocked polyisocyanate. The blocked polyisocyanate composition according to claim 10 or 11, wherein the carboxylate is a carboxylic acid metal salt or a quaternary ammonium cation carboxylate. The blocked polyisocyanate composition according to claim 12, wherein the carboxylic acid salt is a carboxylic acid metal salt. The blocked polyisocyanate composition according to claim 13, wherein the metal species of the carboxylic acid metal salt is a monovalent metal. The blocked polyisocyanate composition according to any one of claims 10 to 14, wherein the compound having a heterocycle containing one or more nitrogen is a compound having a heterocycle containing two or more nitrogen. The blocked polyisocyanate composition according to claim 15, wherein the blocking agent is a compound having a heterocycle containing three or more nitrogens. A resin composition comprising the block polyisocyanate composition according to any one of claims 1 to 16 and a multivalent hydroxy compound. The resin composition according to claim 17, wherein the glass transition temperature Tg of the multivalent hydroxy compound is 0 ° C. or higher and 100 ° C. or lower. The polyvalent weight average molecular weight of the hydroxy compound is 2.0 × 10 ⁵ or less 5.0 × 10 ³ or more, the resin composition according to claim 17 or 18. The resin composition according to any one of claims 17 to 19, wherein the hydroxyl value of the multivalent hydroxy compound is 30 mgKOH / g or more and 250 mgKOH / g or less. The resin composition according to any one of claims 17 to 20, wherein the content of the blocked polyisocyanate is 5 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the polyvalent hydroxy compound. A resin film obtained by curing the resin composition according to any one of claims 17 to 21. A resin film having a thickness of 40 μm obtained by heating and curing the resin composition at 80 ° C. for 30 minutes is stored at 23 ° C. for 1 week and then immersed in acetone at 23 ° C. for 24 hours to have a gel fraction of 80% by mass. The resin film according to claim 22. A resin film having a film thickness of 40 μm, a width of 10 mm and a length of 40 mm, which is obtained by heating the resin composition at 80 ° C. for 30 minutes and curing it, is set so that the distance between chucks is 20 mm, and the process is carried out at a speed of 20 mm / min. The resin film according to claim 22 or 23, wherein the tensile strength in the tensile test is 5 MPa or more. A laminate containing two or more layers of the resin film according to any one of claims 22 to 24 having different compositions.
A laminate having a thickness of 1 μm or more and 50 μm or less per layer of the laminate. A hydrophilic polyisocyanate composition derived from a hydrophilic compound and an alicyclic polyisocyanate having an isocyanurate group.
A hydrophilic polyisocyanate composition in which the ratio of isocyanate groups modified with the hydrophilic compound to the total molar amount of isocyanate groups of the alicyclic polyisocyanate is 2 mol% or more and 15 mol% or less. The hydrophilic polyisocyanate composition according to claim 26, wherein the alicyclic polyisocyanate contains a polyisocyanate having an isocyanurate group derived from isophorone diisocyanate. The hydrophilic polyisocyanate composition according to claim 26 or 27, wherein the alicyclic polyisocyanate has an average number of functional groups of 2.5 or more and 6.0 or less. The hydrophilic polyisocyanate composition according to any one of claims 26 to 28, wherein the hydrophilic polyisocyanate composition has a weight average molecular weight of 900 or more and 20000 or less. The hydrophilic polyisocyanate composition according to any one of claims 26 to 29, wherein the hydrophilic compound is a nonionic compound or an anionic compound. A blocked polyisocyanate composition, wherein at least a part of the isocyanate groups in the hydrophilic polyisocyanate composition according to any one of claims 26 to 30 is sealed with a blocking agent. The blocked polyisocyanate composition according to claim 31, wherein the blocking agent is at least one compound selected from the group consisting of an active methylene compound, an oxime compound, an amine compound, a pyrazole compound, and a triazole compound. .. A resin composition comprising the hydrophilic polyisocyanate composition according to any one of claims 26 to 30 and a polyol. A resin composition comprising the blocked polyisocyanate composition according to claim 31 or 32 and a polyol. A resin film obtained by curing the resin composition according to claim 33 or 34.