JPH0665348A - Acrylic-urethane thermosetting resin composition - Google Patents

Abstract

(57) [Summary] [Structure] An acrylic resin having an active amino group in the molecule obtained by hydrolyzing an acrylic resin obtained by copolymerizing N-vinylformamide with another polymerizable vinyl monomer ( Acrylic-urethane thermosetting resin composition containing A) and a polyurethane resin (B) having a blocked isocyanate group in an equivalent ratio of amino group / blocked isocyanate group = 1/10 to 10/1 And an aqueous acryl-urethane thermosetting resin composition obtained by dispersing the resin in an aqueous medium. [Effect] The acrylic-urethane heat-effective resin composition of the present invention can form a cured coating film having excellent mechanical properties such as weather resistance, strength and flexibility. Therefore, it is extremely useful as a fiber, an adhesive, a coating agent, a vehicle for paints or inks, and the like.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel and useful thermosetting resin composition of an acrylic-urethane resin. More specifically, an acrylic resin (A) having an active amino group in a molecule and a block obtained by hydrolyzing an acrylic resin obtained by copolymerizing N-vinylformamide and another polymerizable vinyl monomer The present invention relates to an acrylic-urethane type thermosetting resin composition containing a polyurethane resin (B) having an isocyanate group.

[0002]

2. Description of the Related Art Conventional polyurethane resins are excellent in mechanical properties such as strength and flexibility of coating films, while acrylic resins are excellent in weather resistance of coating films. Research on acrylic-urethane resins for obtaining films has been carried out in various fields including those for paints and adhesives.

In the solvent system, a two-pack type acrylic-urethane resin in which a polyisocyanate is used as a cross-linking agent in an acrylic resin having a hydroxyl group is well known in the solvent system, and a paint having extremely good properties is also obtained. Has been.

However, the polyisocyanate used as a cross-linking agent is extremely active and gradually reacts with an acrylic resin having a hydroxyl group at room temperature, so that it is used as a two-pack type in which both are compounded before use. In order to avoid the complexity of using such a two-pack type, a method of blocking the active groups of polyisocyanate with an isocyanate group blocking agent and compounding this with an acrylic resin having a hydroxyl group to form a one-pack type is also performed. In this case, a general blocking agent such as an oxime or caprolactam has a slow curability, and the baking conditions tend to be high temperature and long time, and the reaction tends to be insufficient, and its use is limited.

[0005]

As described above, as long as the conventional techniques are followed, it is difficult to obtain a one-component type acrylic-urethane resin composition having extremely high practicality. It can be said that the advent of a one-pack type acrylic-urethane resin aqueous dispersion having good solubility and having excellent mechanical properties of polyurethane resin and weather resistance of acrylic resin is the present demand in the art.

Therefore, the present inventor is based on improving the compatibility of such an acrylic resin and a polyurethane resin, and is excellent in curability. In addition, the excellent mechanical properties of the polyurethane resin and the acrylic resin are excellent. Research has begun to achieve compatibility with weather resistance.

[0007] Therefore, the problem to be solved by the present invention is, in part, to have both the weather resistance of an acrylic resin and the flexibility and strength of a polyurethane resin.
It is to provide a one-pack type acrylic-urethane thermosetting resin composition having extremely high practicality.

Further, if such a composition is obtained, it is emulsified in water, and from the viewpoints of pollution control and environmental pollution control, acryl which is highly practical and has been gaining attention in place of conventional organic solvent-based resins. A urethane resin aqueous dispersion can also be obtained.

[0009]

The inventor of the present invention has completed the present invention as a result of intensive studies and focusing on the problems to be solved by the invention as described above.

That is, according to the present invention, an acrylic resin having an active amino group in a molecule (A) obtained by hydrolyzing an acrylic resin obtained by copolymerizing N-vinylformamide and another polymerizable vinyl monomer (A ) And a polyurethane resin (B) having a blocked isocyanate group, a thermosetting resin composition. Further, the present invention provides a water-based acrylic-urethane thermosetting resin composition obtained by dispersing a composition containing the above-mentioned amino group-containing acrylic resin and blocked isocyanate group-containing polyurethane resin in an aqueous medium. .

Used in carrying out the present invention,
The acrylic resin solution containing N-vinylformamide as a copolymerization component is an acrylic resin solution containing N-vinylformamide and another polymerizable vinyl monomer copolymerizable therewith, such as methyl (meth) acrylate, ethyl (meth) acrylate, ( (Meth) acrylic acid n-butyl, (meth) acrylic acid lauryl ester such as lauryl; (meth) acrylic acid hydroxyethyl, (meth) acrylic acid hydroxypropyl monomers such as hydroxypropyl; acrylamide,
Α such as methacrylamide and n-methyl acrylamide
-Or β-unsaturated amides; acrylonitrile,
Α- or β-unsaturated nitriles such as methacrylonitrile; styrene derivatives such as styrene, α-methylstyrene and vinyltoluene; vinyl esters such as vinyl acetate and vinyl propionate; vinyl chloride, vinylidene chloride, and other fluorine-containing monoesters. It is obtained by copolymerizing vinyl halides such as monomers; or conjugated dienes such as butadiene with one or more monomers.

The content of the formamide group in the thus obtained N-vinylformamide group-containing acrylic resin solution is 0.1 to 100 parts of the acrylic resin solid content.
Must be within 50 copies. When the amount of formamide groups in the acrylic resin solution is lower than 0.1 part per 100 parts of the acrylic resin solid content, the content of amino groups obtained by hydrolysis is low, and as a result, the blocked isocyanate groups to be used next are When the polyurethane resin contained therein is blended, a sufficient crosslinking reaction does not occur, and the physical properties of the finally obtained acrylic-urethane resin coating film deteriorate, which is not preferable. Further, when the amount of formamide groups in the acrylic resin solution exceeds 50 parts per 100 parts of the acrylic resin solid content, the content of amino groups obtained by hydrolysis is high, and as a result, the blocked isocyanate groups to be formed next are contained. When a polyurethane resin is blended, due to a significant crosslinking reaction, the acrylic-urethane resin coating film finally obtained becomes hard but extremely brittle, and this is also where the physical properties of the coating film deteriorate, Not preferable. The preferable amount of formamide group per 100 parts of acrylic resin solid content is in the range of 0.3 to 20 parts, and the amine value of the acrylic resin obtained by hydrolysis is usually 1.0.
Within the range of 150.

The formamide group-containing acrylic resin solution used in the present invention may contain a carboxyl group-containing monomer. The carboxyl group promotes hydrolysis of the formamide group and can form an intramolecular salt with some amino groups. In addition, the carboxyl group serves to disperse a composition containing an amino group-containing acrylic resin and a polyurethane resin having a blocked isocyanate group in an aqueous medium, and is effective in obtaining an aqueous acrylic-urethane thermosetting resin composition. Can work

Specific examples of such a carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid. The amount of the carboxyl group-containing monomer used is preferably 5% by weight or less based on the total monomers. When the amount of the carboxyl group-containing monomer used is more than 5% by weight, the water resistance of the finally obtained acrylic-urethane resin coating film tends to decrease, which is not preferable.

Then, the formamide group-containing acrylic resin solution thus obtained is hydrolyzed to convert the formamide group to an amino group. The hydrolysis reaction of the formamide group proceeds under both an acid catalyst and an alkali catalyst. As the acid, an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or an organic acid such as paratoluenesulfonic acid can be used, and as the alkali, an inorganic alkali such as caustic soda or caustic potash, a trialkylamine, or a trialkylamine. Alkyl alkanolamine,
Trialkanolamine, Triethylenediamine (DA
Organic alkaline substances such as BCO) and 1,8-diazabicyclo (5,4,0) undecene (DBU) can be used. The formamide group-containing acrylic resin solution to which the catalyst has been added is heated to 80 to 150 ° C. The progress of hydrolysis is checked by measuring the amine number in the resin. The hydrolysis of the formamide group to the amino group is carried out in water or an organic solvent. When an organic solvent is used, a lower alcohol having a relatively low boiling point is preferably used.

In the present invention, the thus obtained acrylic resin containing an active amino group in the molecule is blended with a polyurethane resin having a blocked isocyanate group to prepare the thermosetting resin composition of the present invention.

The polyurethane resin having a blocked isocyanate group suitable for the present invention is prepared by reacting a polyol component with a stoichiometric excess of an organic isocyanate compound, and a known isocyanate blocking agent is added to an isocyanate group-terminated polyurethane resin. Made by.

The organic polyisocyanate compounds which can be used in the production of the polyurethane resin used in the present invention are not particularly limited but only 2,4.
-Tolylene diisocyanate, 2,6-Tolylene diisocyanate, m-Phenylene diisocyanate, p-Phenylene diisocyanate, 4,4'-Diphenylmethane diisocyanate, 2,4'-Diphenylmethane diisocyanate, 2,2'-Diphenylmethane diisocyanate , 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-
Biphenylene diisocyanate, 3,3'-dichloro-
4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene di Isocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate
, Xylylene diisocyanate, tetramethyl xylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate Examples thereof include net or 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate.

The polyol component that can be used is generally linear and has an average molecular weight of 300 to 20,000, preferably 500 to 4,000. Examples of such compounds include a hydroxyl group, a carboxyl group, an amino group or a mercapto group at the terminal, for example, polyester,
Examples thereof include polyacetals, polyethers, polythioethers, polyhydroxy compounds such as polyamides and polyesteramides.

As the polyester polyol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol,
1,6-hexanediol, neopentyl glycol,
Diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (molecular weight 300 to 6,000), dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, glycol components such as hydrogenated bisphenol A, hydroquinone and their alkylene oxide adducts, and succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid Acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4
Of naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p′-dicarboxylic acid and these dicarboxylic acids Anhydrides or ester-forming derivatives; other polyesters obtained by dehydration condensation reaction with acid components such as p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and ester-forming derivatives of these hydroxycarboxylic acids Examples thereof include polyesters obtained by a ring-opening polymerization reaction of a cyclic ester compound such as ε-caprolactone and copolymerized polyesters thereof.

As the polyether, ethylene glycol, diethylene glycol, triethylene glycol,
Propylene glycol, trimethylene glycol, 1,
3-butanediol, 1,4-butanediol, 1,6
-Hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, sorbitol, sucrose, aconit sugar, trimellitic acid, hemimellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, triisopropanolamine, pyrogallol, dihydroxybenzoic acid, hydroxy Ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran using one or more compounds having at least two active hydrogen atoms such as phthalic acid and 1,2,3-propanetrithiol as an initiator. , And cyclohexylene and the like, and those obtained by addition-polymerizing one or more monomers by a conventional method.

As the polycarbonate polyol,
1,4-butanediol, 1,6-hexanediol,
Examples thereof include compounds obtained by reacting a glycol such as diethylene glycol with diphenyl carbonate or phosgene.

Other polyhydroxy compounds containing urethane or urea groups as well as natural polyols, including optionally modified ones such as castor oil and carbohydrates, can also be used.

The polyol component having an average molecular weight of 300 to 20,000 according to the present invention comprises a high molecular weight polyol and a molecular weight of 300.
The following low molecular weight compounds are mixed to give an average molecular weight of 300-
Of course, it can be set to 20000. Suitable low molecular weight compounds are compounds having a molecular weight of 300 or less and containing at least two or more active hydrogens, for example, a glycol component used as a raw material of polyester polyol; glycerin, trimethylolethane, trimethylolpropane, sorbitol. , And polyhydroxy compounds such as pentaerythritol.

When the thermosetting resin composition obtained in the present invention is made into an aqueous system, it can be obtained by a conventionally known method for making an aqueous urethane resin aqueous. That is, generally, a polyurethane resin containing a hydrophilic group in the molecule and containing an isocyanate group is reacted with an isocyanate blocking agent to be made water-based.

A polyurethane resin containing a hydrophilic group in the molecule and containing an isocyanate group means at least one active isocyanate group in one molecule and a carboxyl group, a sulfone group, a phosphoric acid group, an amino group or ethylene as a hydrophilic group. It is a polyurethane resin having one or more groups selected from oxide repeating units, and is characterized by having reactivity and being capable of self-emulsification in water.

Here, at least one active isocyanate in one molecule and one or more groups selected from repeating units of carboxyl group, sulfone group, phosphoric acid group, amino group and ethylene oxide as hydrophilic groups are used. The polyurethane resin has can be obtained, for example, by reacting a polyol component containing a hydrophilic group with at least one organic polyisocyanate compound having two or more isocyanate groups in one molecule.

Examples of the polyol component having one or more groups selected from the repeating units of a carboxyl group, a sulfone group, a phosphoric acid group, an amino group and ethylene oxide as a hydrophilic group include, for example, dimethylolpropionic acid and Use of a polyol compound having a carboxylic acid group having poor reactivity with an isocyanate group such as diethylolpropionic acid, or a polyol compound or phosphoric acid obtained by condensing a compound having a sulfonic acid group such as sodium sulfone dimethylisophthalate A method using a group-containing polyol,
Alternatively, it can be obtained by using a nitrogen-containing hydroxyl compound such as N-methyldiethanolamine or N-ethyldiethanolamine, or by using a hydrophilic polyol such as polyethylene glycol or polyethylene glycol monoalkyl ether.

Examples of the polyol component which can be used in combination with such a hydrophilic polyol include ethylene glycol-
, Propylene glycol, 1,3-propanedioe
1,4-butanediol, 1,5-pentanediol
3-methyl-1,5-pentanediol, 1,6-
Hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a molecular weight of 200 to 6,000, dipropylene glycol, tripropylene glycol , Bishydroxyethoxybenzene,
Low such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, glycerin, trimethylolpropane, sorbitol or pentaerythritol. Examples thereof include molecular weight polyhydroxy compounds.

An aqueous polyurethane resin containing the above-mentioned hydrophilic group in the molecule and containing an isocyanate group is prepared by blocking an active isocyanate group with a blocking agent, and then by the action of the hydrophilic group contained in the polyurethane resin, an aqueous medium is obtained. Dispersed in. As a method of water dispersion at this time, a polyurethane resin having a blocked isocyanate group is a group capable of forming a salt such as a carboxyl group or a sulfonic acid group in an amount sufficient to form a stable aqueous dispersion. In the case of having a carboxyl group or sulfonic acid group in the form of a salt, a soap-free aqueous polyurethane resin dispersion can be obtained. 16-18 polyoxyethylene nonylphenol ether or polyoxyethylene-
By using a nonionic emulsifier such as an oxypropylene block copolymer; or a known conventional surfactant such as an anionic emulsifier such as sodium lauryl sulfate or soda dodecylbenzenesulfonate, phase inversion emulsification is performed. Alternatively, a polyurethane resin aqueous dispersion that can be used in the present invention can be obtained by carrying out mechanical emulsification using a colloid mill or the like.

In the polyurethane resin having a blocked isocyanate group of the present invention, a low molecular weight polyamine compound may be used in combination mainly for the purpose of increasing the molecular weight of the polyurethane resin.

As such polyamine compounds, only typical ones will be exemplified. Ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2,
5-dimethylpiperazine, isophoronediamine, 4,
4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine,
Examples include diamines such as 1,4-cyclohexanediamine; polyamines such as diethylenetriamine, dipropylenetriamine, and triethylenetetramine; or hydrazines. In addition to these low molecular weight polyamines, derivatives in which the above-mentioned low molecular weight polyamines are reacted with a polyepoxide compound in an amount less than the stoichiometric amount and the end group of which is an amine are also preferable. Can be used.

In the present invention, conventionally known isocyanate blocking agents can be used. For example, oximes such as formaldoxime, acetoaldoxime, propionaldoxime, butylaldoxime, benzaldoxime, acetophenone oxime, methylethylketoxime, cyclohexanone oxime, phenol, ortho-chlorophenol, and meta-cresol. Examples thereof include phenols, lactams such as epsilon-caprolactam, and compounds such as diethyl malonate. Of these, particularly preferred are oximes represented by methylethylketoxime.

The polyurethane resin having a blocked isocyanate group in the molecule which is usually used in the present invention is a polyurethane resin having an isocyanate group in the molecule,
It can be obtained by dropping an isocyanate blocking agent. Further, in order to uniformly carry out the reaction, a polyurethane resin having a blocked isocyanate group is prepared with respect to an isocyanate group such as dioxane, acetone, methyl ethyl ketone, acetonitrile, ethyl acetate, tetrahydrofuran, toluene and xylene. Active organic solvents are used. This organic solvent is usually used in an amount of 20 to 100% (% by weight) based on the solid content of the polyurethane resin. When the amount of the organic solvent is less than 20% based on the solid content of the polyurethane resin, the viscosity of the polyurethane resin solution is generally too high, and the handling tends to be difficult, which is not preferable. When the amount of organic solvent is more than 100% based on the solid content of polyurethane resin, workability is not improved even if the amount of organic solvent is increased further.
It is also uneconomical because the amount of solvent to be volatilized increases.

Polyurethane resin (B) having a blocked isocyanate group in acrylic resin (A) containing an active amino group in the molecule obtained by hydrolyzing an acrylic resin containing N-vinylformamide as a copolymerization component of the present invention. The ratio of the amino group-containing acrylic resin (A) and the blocked isocyanate group-containing polyurethane resin (B) of the thermosetting resin composition containing the above is an equivalent ratio of amino group / blocked isocyanate group = 1/10 to 10 It is / 1. Even if there are less amino groups than amino groups / blocked isocyanate groups = 1/10, or if there are more amino groups than amino groups / blocked isocyanate groups = 10/1, an effective cross-linking reaction does not occur, which is not preferable. Amino group / blocked isocyanate group = 1/5 to 5/1 is preferable.

The acrylic-urethane type thermosetting resin composition of the present invention is a one-pack type and has excellent weather resistance and mechanical properties. Further, by emulsifying in water, it is possible to obtain an acrylic-urethane resin aqueous dispersion excellent in pollution control and environmental pollution control.

The acrylic-urethane type thermosetting resin composition of the present invention is applied by spray coating, roll coating or the like to obtain a good coating film. A resin, a two-pack type acrylic-urethane thermosetting resin composition, or the like can be used for many applications that could not be achieved.

That is, coatings for vehicles such as inks, metallic bases for automobiles, automotive coatings such as intermediate coatings and household coatings, glass, plastics, fabrics, paper, leather, wood or metal; fibers and fabrics. Thin-film coating to fur; surface coating for fur, etc.
Further, it can be used in a wide range of applications as various adhesives and the like.

[0039]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[Synthesis of Acrylic Resin Having Amino Group] Synthesis Example 1 Isopropyl alcohol (hereinafter referred to as IPA) was used as a solvent in a 2 liter flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and an inert gas inlet. 700 parts are charged and the temperature is raised to 80 ° C. in a nitrogen gas stream. Separately, 441 parts of methyl methacrylate, 210 parts of butyl acrylate, and 49 parts of N-vinylformamide were weighed and mixed in advance as vinyl monomers, and the same azobisisobutyronitrile 1 was used.
4 parts are weighed, injected from separate dropping ports, and dropwise polymerized for 3 hours. After that, the temperature was kept at the same temperature for 5 hours to obtain a uniform resin solution. 20 parts of triethylamine was added to the obtained resin solution and the mixture was kept at the same temperature for 5 hours to hydrolyze the formamide group.

The resulting acrylic resin solution (hereinafter referred to as acrylic resin A-1) had a nonvolatile content of 52.2% and a viscosity of 120.
From IR analysis and NMR analysis at 0 cps, it was confirmed that about 80% of the N-vinylformamide used was changed to amine, the nonvolatile content was 50.2%, and the polyacrylate having an amine value of 22.6. Was obtained.

Synthesis Example 2 700 parts of butyl cellosolve are charged in the same apparatus as in Synthesis Example 1 and heated to 110 ° C. in a nitrogen gas stream. Separately, 210 parts of styrene, 252 parts of methyl methacrylate, 210 parts of butyl acrylate, 21 parts of methacrylic acid, and 7 parts of N-vinylformamide were separately weighed in advance as vinyl monomers, and 10 parts of azobisvaleronitrile were similarly weighed. It is injected from another dropping port and polymerized dropwise for 4 hours. After that, the temperature was kept at the same temperature for 5 hours to obtain a uniform resin solution. The obtained resin solution was cooled to 80 ° C., 10 parts of sodium hydroxide was added, and the mixture was stirred at the same temperature for 5 hours to hydrolyze the formamide group. The obtained acrylic resin solution (hereinafter referred to as acrylic resin A-2) had a nonvolatile content of 50.
It was found that a polyacrylate having an amine value of 3.7, which was 9%, was obtained.

Synthesis Example 3 700 parts of butyl cellosolve was charged in the same apparatus as in Synthesis Example 1 and heated to 110 ° C. in a nitrogen gas stream. Separately, 105 parts of styrene as a vinyl monomer, 420 parts of butyl methacrylate, 35 parts of acrylonitrile, 35 parts of polyoxyethylene methyl ether methacrylate (polyoxyethylene partial molecular weight of about 1600), and 105 parts of N-vinylformamide were weighed and mixed in advance. Similarly, 10 parts of azobisisobutyronitrile is weighed, injected from separate dropping ports, and then dropped and polymerized for 4 hours. After that, the temperature was kept at the same temperature for 5 hours to obtain a uniform resin solution. The obtained resin solution was cooled to 60 ° C., 210 parts of water in which 13 parts of 25% ammonia water was dissolved was added, and the mixture was stirred at the same temperature for 5 hours to hydrolyze the formamide group. The obtained acrylic resin (hereinafter referred to as acrylic resin A-3) had a nonvolatile content of 43.4%, and it was confirmed that a polyacrylate having an amine value of 50.5 was obtained.

Synthesis Example 4 700 parts of toluene was charged in the same apparatus as in Synthesis Example 1, and the temperature was raised to 105 ° C. in a nitrogen gas stream. Separately, 350 parts of styrene and 14 parts of butyl methacrylate as vinyl monomers.
0 parts, 2-ethylhexyl acrylate 70 parts, and N-vinylformamide 140 parts were weighed and mixed in advance, 10 parts of azobisisobutyronitrile were weighed in the same manner, and each was injected from another dropping port and added dropwise for 4 hours. Polymerize. After that, the temperature was kept at the same temperature for 5 hours to obtain a uniform resin solution. The obtained resin solution was cooled to 60 ° C., and a toluene solution 210 containing 13 parts of p-toluenesulfonic acid was dissolved.
Part was added and stirred at the same temperature for 5 hours to hydrolyze the formamide group. The resulting acrylic resin (hereinafter referred to as acrylic resin A-4) has a nonvolatile content of 42.7% and 59.
It was found that a polyacrylate having an amine number of 5 was obtained.

[Synthesis of Polyurethane Resin Having Blocked Isocyanate Group] Synthesis Example 5 First, 1,6-hexanediol-neopentyl glycol-adipic acid-polyester (OH value was placed in a flask equipped with a thermometer, a stirrer and a reflux condenser. 102) to 550
Parts, dehydration under reduced pressure at 120 to 130 ° C., then cooling to 50 ° C., adding 1270 parts of methyl ethyl ketone (hereinafter referred to as MEK), thoroughly stirring and mixing, and then 250
Part of 4,4'-diphenylmethane diisocyanate was added, and the mixture was heated to 70 ° C and reacted at this temperature for 2 hours to give 5
Cool to 0 ° C., add 26 parts of neopentyl glycol, and continue stirring at the same temperature for 6 hours. Next, 43 parts of methyl ethyl ketoxime was added dropwise, and stirring was continued at the same temperature for 1 hour to obtain a nonvolatile content of 41.2% and a Gardner viscosity of O.
To P, a pale yellow transparent block isocyanate group-containing polyurethane resin solution (hereinafter referred to as polyurethane resin B-
I got 1).

Synthesis Example 6 Polycarbonate diol (O
H value 56) is added to 600 parts, and the pressure is reduced to 120 to 130 ° C.
Dehydration, then cooled to 50 ° C and 833 parts ME
After K was added and thoroughly mixed with stirring, 500 parts of isophorone diisocyanate was added and heated to 70 ° C., reacted at this temperature for 2 hours, cooled to 50 ° C., 59 parts of 1,6-hexanediol and trimethylolpropane. And 18 parts of dimethylolpropionic acid and 67.5 parts of dimethylolpropionic acid are added, and the mixture is further added at the same temperature for 3 times.
Continue stirring for hours. Next, 130 parts of methyl ethyl ketoxime is added dropwise and stirring is continued at the same temperature for 1 hour.
A light yellow transparent solution having a nonvolatile content of 62.6% and a Gardner viscosity of Z2 (hereinafter referred to as polyurethane resin (hereinafter referred to as polyurethane resin B-2) was obtained.

Synthesis Example 7 A 2/1 molar ratio reaction product (OH value 84) of flaxseed oil fatty acid and trimethylolpropane was placed in the same apparatus as in Synthesis Example 5.
8 parts, 125 parts of polytetramethylene ether glycol (OH value 224) were added, dehydration was performed at 120 to 130 ° C. under reduced pressure, then cooled to 50 ° C., 550 parts of MEK was added and sufficiently stirred and mixed, and then 4,4 ′. -Add 425 parts of dicyclohexylmethane diisocyanate, heat to 70 ° C, react at this temperature for 2 hours, cool to 60 ° C, add 66 parts of 3-methyl-1,6-hexanediol, and stir at the same temperature for another 3 hours. continue. Then, 141 parts of ε-caprolactam is added, and the mixture is further reacted at the same temperature for 5 hours. A yellow viscous liquid having a nonvolatile content of 72.8% and a Gardner viscosity of Z6 to Z7 (hereinafter referred to as polyurethane resin B-3) was obtained.

Examples 1 to 9 Thermosetting compositions of acrylic resin and polyurethane were prepared with the compounding ratios (shown in parts) as shown in Tables 1 and 2.

Application Example 1 Next, a white paint having a PWC of 40% was prepared from this thermoplastic composition, and then toluene / xylene / n-butanol / cellosolve acetate = 40/20/30/10.
Dilute to a spray viscosity with a mixed solvent (weight ratio),
Each zinc phosphate-treated steel plate was spray-coated so that the dry film thickness was about 50 μm, and then baked at 80 ° C. for 20 minutes to obtain each cured coating film. The weather resistance was evaluated by exposing each of the coating films thus obtained to outdoor exposure in Miyazaki for 2 years. The results are summarized in Tables 1 and 2.

[0050]

[Table 1] * 1: Rutile titanium oxide manufactured by Ishihara Sangyo Co., Ltd. * 2: Value obtained by dividing the gloss value of the coating film after exposing the cured coating film in Miyazaki prefecture for 2 years by the gloss value before exposure and multiplying by 100. The larger this value is, the better the weather resistance is.

* 3: Erichsen value (mm)

[0052]

[Table 2] Example 10 174 parts of the acrylic resin solution of Synthesis Example 4 and 40 parts of the polyurethane resin solution of Synthesis Example 6 were mixed, 150 parts of water was added dropwise, and MEK was distilled off under reduced pressure to give a nonvolatile content of 34.6%. A bluish milky white dispersion of water was obtained. The stability of this aqueous dispersion was extremely good, and no sedimentation or separation was observed even after 1 month.

Application Example 2 The above aqueous dispersion was applied to a zinc phosphate-treated steel sheet to give a dry film thickness of about 50 μm.
It was confirmed that a tough coating film having a pencil hardness H and an Erichsen value of 7 mm or more can be obtained by coating with a roll coater so as to obtain and then baking at 80 ° C. for 20 minutes. The weather resistance was also extremely excellent.

Comparative Example 1 As a comparative example, a commercially available acrylic polyol and a polyfunctional polyisocyanate were combined to prepare a coating composition.
This formulation became thick and unusable after about 1 day.

Comparative Example 2 A coating composition was prepared in which the polyfunctional polyisocyanate of Comparative Example 1 was blocked with a blocking agent for the purpose of improving coating stability. Although the paint stability of this paint formulation is maintained for one month, the formulation is diluted to a spray viscosity with a mixed solvent as in the example, and spray-coated on a zinc phosphate-treated steel sheet so that the dry film thickness is about 50μ. Then, even after baking at 140 ° C. for 20 minutes, it was not cured and a coating film could not be obtained.

[0056]

The acrylic-urethane type heat-effective resin composition of the present invention can form a cured coating film having excellent mechanical properties such as weather resistance, strength and flexibility. Therefore, they are extremely useful as fibers, adhesives, coating agents, vehicles for paints or inks, and the like.

Claims (4)

[Claims] 1. An acrylic resin (A) having an active amino group in a molecule and a block obtained by hydrolyzing an acrylic resin obtained by copolymerizing N-vinylformamide and another polymerizable vinyl monomer. An acrylic-urethane thermosetting resin composition containing a polyurethane resin (B) having an isocyanate group. 2. A ratio of the acrylic resin (A) having an active amino group in the molecule to the polyurethane resin (B) having a blocked isocyanate group in the molecule is equivalent to amino group / blocked isocyanate group = 1/10 to 10 It is / 1, The acrylic-urethane type thermosetting resin composition of Claim 1 characterized by the above-mentioned. 3. An acrylic resin (A) having an active amino group in the molecule and a block obtained by hydrolyzing an acrylic resin obtained by copolymerizing N-vinylformamide with another polymerizable vinyl monomer. A water-based acrylic-urethane thermosetting resin composition obtained by dispersing a polyurethane resin (B) having an isocyanate group in an aqueous medium. 4. The polyurethane resin (B) has one or more hydrophilic groups selected from the group consisting of a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a repeating unit of ethylene oxide. The water-based acrylic-urethane thermosetting resin composition according to claim 3.