JP2003192761A - Acrylic-modified urethane resin composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acrylic-modified urethane resin composition soluble in an organic solvent having excellent adhesion to various plastic materials, weather resistance, mechanical strength, chemical resistance, and stain resistance. SOLUTION: Radical polymerization containing 1 to 99% by weight of a urethane resin obtained by reacting at least an organic diisocyanate, a high molecular weight polyol and a chain extender, and 1,4-cyclohexanedimethanol mono (meth) acrylate as essential components Unsaturated monomer 99-1% by weight
And an acrylic-modified urethane resin composition obtained by copolymerizing

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an acrylic modified urethane resin composition. More specifically, the present invention relates to an acrylic-modified urethane resin having excellent adhesion to various plastic materials, good solution properties, and good mechanical strength, weather resistance, chemical resistance, and stain resistance of the resulting coating film.

[0002]

Urethane resin has good flexibility, abrasion resistance, oil resistance, chemical resistance, adhesiveness, etc., while acrylic resin has weather resistance, heat resistance, hydrolysis resistance, chemical resistance. Due to their excellent properties, they are widely used in paints, inks, adhesives, and other coating agent applications. However, the urethane resin and the acrylic resin have poor compatibility with each other, and when used as a mixture, they have drawbacks such as stability of the solution and poor coating film properties after drying. Therefore, the inventors of the present invention disclosed in Japanese Unexamined Patent Publication No. H9-268215 a combination of two or more active hydrogens and one or more radically polymerizable double bonds as a means for improving the compatibility between the urethane resin and the acrylic resin. We have proposed an acrylic copolymer-modified urethane resin that is soluble in a solution and has excellent compatibility by using a compound containing a double bond in the same molecule. Further, for example, Japanese Patent Publication No. 55528/1993 discloses an attempt to form a composite by copolymerizing a urethane resin macromer and an acrylic monomer. Further, in JP-A-5-262846,
A composite technology of reacting an acrylic macromer having a hydroxyl group with a urethane resin has also been proposed. However, the radically polymerizable monomers conventionally used in these methods have limitations in mechanical strength, weather resistance, chemical resistance and stain resistance.

[0003]

The object of the present invention is to have a wide range of adhesiveness to various plastic materials, weather resistance,
Form a coating with high mechanical strength, chemical resistance, and stain resistance,
Another object of the present invention is to provide an acrylic-modified urethane resin composition which is soluble in an organic solvent and has a good solution property, which is suitable for inks, paints and other coating applications, and a method for producing the same.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that an acrylic resin obtained by reacting a urethane resin with a specific radically polymerizable unsaturated monomer. The modified urethane resin composition has a wide range of adhesion to various plastic materials, forms a coating film with high weather resistance, mechanical strength, chemical resistance, and stain resistance, and is a good solution that is soluble in organic solvents. The present invention has been completed by finding that a resin solution having a proper property is provided. That is, the first aspect of the present invention
The gist of is a radical polymerization using 1-99% by weight of a urethane resin obtained by reacting at least an organic diisocyanate, a high molecular weight polyol and a chain extender, and 1,4-cyclohexanedimethanol mono (meth) acrylate as an essential component. An acrylic-modified urethane resin composition, which is obtained by copolymerizing 99 to 1% by weight of a polyunsaturated monomer.

The second aspect of the present invention is to contain a radical-polymerizable double bond having an organic diisocyanate, a high-molecular weight polyol, one or more active hydrogens and one or more radical-polymerizable double bonds in the same molecule. A compound and a chain extender are reacted to form a radically polymerizable double bond at 1 to 200 μeq.
/ G, and the weight average molecular weight is 10,000 to 20,000
Radical-polymerizable unsaturated monomer containing 0-radical-polymerizable double bond-containing urethane resin as an essential component and 1-99% by weight of the urethane resin and 1,4-cyclohexanedimethanol mono (meth) acrylate The method for producing an acrylic-modified urethane resin composition is characterized by radically reacting with 99 to 1% by weight.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION <Acrylic-modified urethane resin composition> The acrylic-modified urethane resin composition of the present invention contains 1 to 99 parts by weight of a urethane resin obtained by reacting at least an organic diisocyanate, a high molecular weight polyol and a chain extender. % And 99 to 1% by weight of a radically polymerizable unsaturated monomer containing 1,4-cyclohexanedimethanol mono (meth) acrylate as an essential component.

The organic diisocyanate used in the present invention includes hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate (IPDI), 4, 4'-methylenebis (cyclohexyl isocyanate) (H12MD
I), alicyclic diisocyanates such as ω, ω′-diisocyanate dimethylcyclohexane, aliphatic diisocyanates having an aromatic ring such as xylylene diisocyanate and tetramethylxylylene diisocyanate, p-phenylene diisocyanate, tolylene diisocyanate (T
DI), 4,4'-diphenylmethane diisocyanate (MDI), naphthalene-1,5-diisocyanate,
Examples thereof include aromatic diisocyanates such as trisine diisocyanate and the like, and mixtures of two or more kinds thereof. Among them, IPDI is preferable for applications requiring weather resistance,
H12 MDI, and T when mechanical strength is required
DI and MDI are preferred.

Examples of the high molecular weight polyol include polyether glycol, polyester glycol, polyether ester glycol, polycarbonate glycol, polyolefin glycol and silicone polyol. Examples of the polyether glycol include those obtained by ring-opening polymerization of cyclic ethers, such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like. As the polyester glycol, dicarboxylic acid (succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, etc.) or an anhydride thereof and a low molecular weight diol (ethylene glycol, diethylene glycol, triethylene glycol, Propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, polytetramethylene glycol, 1,5-pentanediol, 1,6-
Hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-ethyl-1,3-
Hexane glycol, 2,2,4-trimethyl-1,3
-Pentanediol, 3,3-dimethylolheptane,
Those obtained by polycondensation with 1,9-nonanediol, 2-methyl-1,8-octanediol, cyclohexanedimethanol, bishydroxyethoxybenzene, etc., such as polyethylene adipate, polypropylene adipate, polybutylene adipate, polyhexa Examples include methylene adipate, polybutylene sebacate and the like, which are obtained by ring-opening polymerization of lactone to a low molecular weight diol, such as polycaprolactone and polymethylvalerolactone. Examples of the polyether ester glycol include polyester glycol obtained by ring-opening polymerization of cyclic ether with polyester glycol, polycondensation of polyether glycol and dicarboxylic acid, such as poly (polytetramethylene ether) adipate.

Polycarbonate glycols include polybutylene carbonate, polyhexamethylene carbonate, poly (3-methyl-1,5-pentylene) carbonate obtained by deglycolization or dealcoholization from a low molecular weight diol and alkylene carbonate or dialkyl carbonate. Can be mentioned. Examples of the polyolefin polyol include polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol and the like. Examples of the silicone polyol include polydimethylsiloxane polyol. Further, a mixture of two or more of these may be mentioned. The molecular weight of the high molecular weight polyol is usually 200 to 10,000, preferably 5
It is from 00 to 6000. If the molecular weight is too small, the flexibility is poor, and if it is too large, the mechanical strength tends to decrease.

The reaction charge of diisocyanate and high molecular weight polyol is usually 1.01-1 in terms of NCO / OH molar ratio.
It is 0, preferably 1.5 to 5. If this ratio is too small, the amount of hard segment tends to be small and the mechanical strength tends to be low. On the other hand, if it is too large, the solubility tends to be poor and the viscosity tends to increase. As the chain extender, a low molecular weight diol or a low molecular weight diamine is typically used. Examples of the diol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, polytetramethylene glycol, 1,5-pentane. Diol, 1,6-hexanediol, 3-methyl-
1,5-pentanediol, neopentyl glycol,
2-ethyl-1,3-hexane glycol, 2,2,4
Aliphatic diols such as -trimethyl-1,3-pentanediol, 3,3-dimethylolheptane, 1,9-nonanediol, 2-methyl-1,8-octanediol,
Examples thereof include alicyclic diols such as cyclohexanedimethanol, bishydroxyethoxybenzene, bishydroxyethyl terephthalate, aromatic diols such as bisphenol-A, dialkanolamines such as N-methyldiethanolamine, and the like. As diamine, ethylenediamine, propylenediamine, hydrazine, 2,4,4-
Aliphatic diamines such as trimethylhexamethylenediamine, piperazine, cyclohexanediamine, mensendiamine, isophoronediamine, alicyclic diamines such as 4,4′-methylenebis (cyclohexylamine), and the like, and mixtures of two or more thereof. . Further, some of polyols such as trimethylolpropane and glycerin can be used together. Furthermore, in order to control the molecular weight, it is possible to partially substitute monoamine or monoalcohol. As the monoamine, methylamine, ethylamine, butylamine, dibutylamine, ethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1-propanol, 2-amino-2-methyl- 1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, trishydroxymethylaminomethane and the like can be mentioned. Examples of the monoalcohol include methanol, ethanol, propanol, butanol, hexanol and the like.

In the present invention, 1,4-cyclohexanedimethanol mono (meth) acrylate is used as an essential component as a radically polymerizable unsaturated monomer. The ratio of 1,4-cyclohexanedimethanol mono (meth) acrylate in the total amount of radical-polymerizable unsaturated monomer is usually in the radical-polymerizable unsaturated monomer depending on the required hydroxyl value and mechanical strength. It is used in the range of 1 to 100% by weight. Preferably, it is 5 to 90% by weight, more preferably 10 to 70%.
% By weight. If the amount of 1,4-cyclohexanedimethanol mono (meth) acrylate is too small, the effects of improving weather resistance and mechanical strength may not be sufficiently obtained.

Other radically polymerizable unsaturated monomers used in the present invention include styrene, α-methylstyrene, p
-Styrene-based monomers such as methylstyrene and p-chlorostyrene, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Lauryl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate,
Examples thereof include (meth) acrylic monomers such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, and mixtures of two or more thereof. The selection of the radical-polymerizable unsaturated monomer used in combination is made according to the type of material used.

Further, the radical polymerization product of 1,4-cyclohexanedimethanol mono (meth) acrylate and other radically polymerizable unsaturated monomer can be copolymerized by reacting with a urethane resin raw material. . For example, JP-A-5-262847 introduces a method in which a terminal dihydroxy macromonomer is reacted with an organic diisocyanate compound using a mercaptan chain transfer agent having two hydroxyl groups and one mercapto group. In this case, the mercaptan chain transfer agent is 1-
Mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, thioglycerin, 2-mercapto-1,2-propanediol, 2-mercapto-
2-Methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3- Examples thereof include propanediol and 2-mercaptoethyl-2-ethyl-1,3-propanediol. It is also possible to preliminarily polymerize a monomer having a radically polymerizable unsaturated bond such as methacryloyloxyethyl isocyanate and an isocyanate group in the same molecule and use it as a macromer.

The acrylic modified urethane resin composition of the present invention is obtained by polymerizing a radically polymerizable unsaturated monomer with the urethane resin obtained by reacting at least the above-mentioned organic diisocyanate, high molecular weight polyol and chain extender. To be The molecular weight of the urethane resin is 100.
00-200000, preferably 15000-1
50,000, more preferably 20,000 to 10,000
It is 0. If the weight average molecular weight is too small, the flexibility is low and the chemical resistance is poor. On the other hand, if the weight average molecular weight is too large, the compatibility with the acrylic component may be poor and the solution properties may deteriorate, or the solution viscosity may be extremely high, resulting in poor coating workability. The weight ratio of the urethane resin to the radically polymerizable unsaturated monomer is 1/99 to 99/1, preferably 10/90 to 90/10. If this weight ratio is too small, the effect of modifying the urethane resin will be small, and if it is too large, the original properties of the urethane resin will tend to be impaired.

The weight average molecular weight of the acrylic modified urethane resin composition of the present invention is usually 15,000 to 300,000.
And preferably 15,000 to 100,000, more preferably 20,000 to 80,000. If the weight average molecular weight is too small, the strength and chemical resistance of the resulting coating film will be low, and if it is too large, the re-solubility will be lowered, and the solution viscosity will be remarkably increased, whereby workability tends to be lowered. Also,
The acrylic modified urethane resin composition of the present invention is characterized by being soluble in an organic solvent. In the present invention, "soluble in an organic solvent" means that the resin solid content in methyl ethyl ketone is 20% by weight, and the residue when heated at 75 ° C for 10 hours is 0% by weight.

<Method for Producing Acrylic-Modified Urethane Resin Composition> The acrylic-modified urethane resin composition of the present invention can utilize the several methods exemplified above, among which, Japanese Patent Publication No. 55555/1993. 9-268215
In the presence of a urethane resin containing a radical-polymerizable double bond described in Japanese Patent Publication No. 1,4-cyclohexanedimethanol mono (meth) acrylate of the present invention as a radical-polymerizable unsaturated monomer The method of obtaining is simple. Examples of the method for producing a urethane resin containing a radically polymerizable double bond include organic diisocyanates, high molecular weight polyols, radical polymerization having one or more active hydrogens and one or more radically polymerizable double bonds in the same molecule. And a compound having a sex double bond and a chain extender. Here, the organic diisocyanate, the high molecular weight polyol and the chain extender are as described above.

Examples of the radical-polymerizable double bond-containing compound having at least one active hydrogen and at least one radical-polymerizable double bond in the same molecule include allyl alcohol, allylamine and 2-hydroxyethyl (meth). Acrylate, 2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, glycerin monoallyl ether, trimethylolpropane mono (meth) acrylate, etc., and ε-caprolactone adducts, γ-methylvalerolactone adducts thereof, Examples thereof include ethylene oxide adducts and propylene oxide adducts.
The radical-polymerizable double bond-containing compound used here is 1
As long as it has one or more active hydrogens, it may overlap with the radically polymerizable unsaturated monomer described above. Also, a mixture of two or more of these may be used. In particular, by using a compound having two or more active hydrogens and one or more radically polymerizable double bonds in the same molecule, a pendant radically polymerizable double bond is introduced into the urethane resin main chain. It is possible to introduce a polymer into the polyurethane chain as a pendant graft chain,
It is effective to make up for the defects with acrylic resin by taking advantage of the original properties of urethane resin.

The content of the radically polymerizable double bond in the urethane resin is 1 to 200 μeq / g, preferably 1
0 to 150 μeq / g, more preferably 20 to 100
μeq / g. If the double bond content is too low,
The compatibility is insufficient, resulting in poor solution properties and coating film properties. Further, if the content of the double bond is too large, the proportion of the bifunctional urethane resin in the reaction is high, and there is a tendency that three-dimensionalization tends to occur during radical polymerization.

During the urethanization reaction, a polymerization inhibitor can be used to prevent thermal polymerization of the radically polymerizable double bond. As a polymerization inhibitor, methyl hydroquinone, t-
Examples thereof include phenolic compounds such as butylcatechol and chloranil, amines such as diphenylpicrylhydrazine and diphenylamine, and high valent metal salts such as ferric chloride and cupric chloride.

The radical-polymerizable double bond-containing urethane resin of the present invention is produced by a known method, such as a one-shot method,
It is carried out by a prepolymerization method or the like. As a solvent when producing a urethane resin, usually, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, ethyl acetate, butyl acetate, ester such as cellosolve acetate, hydrocarbons such as benzene, toluene, xylene, hexane , Some alcohols such as diacetone alcohol, isopropanol, secondary butanol, and tertiary butanol, chlorides such as methylene chloride and dichloroethane, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, dimethyl sulfoxide, N- Aprotic polar solvents such as methylpyrrolidone and the like, and mixtures of two or more kinds thereof are used.

As the catalyst for producing the urethane resin, a usual urethanization reaction catalyst is used. For example, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stannous octoate and other tin-based, iron acetylacetonate, ferric chloride and other iron-based,
Examples include tertiary amines such as triethylamine and triethylenediamine.

The urethane resin obtained by the above method is added to the above-mentioned 1,4-cyclohexanedimethanol mono (meth)
A radically polymerizable unsaturated monomer containing acrylate as an essential component is reacted. The weight ratio of the urethane resin to the radically polymerizable unsaturated monomer is 1/99 to 99/1,
It is preferably 10/90 to 90/10.

Polymerization is carried out by an ordinary solution polymerization method under a stream of an inert gas such as nitrogen by adding a polymerization initiator in an organic solvent and heating. Examples of the organic solvent used include methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, ethyl acetate, butyl acetate, esters such as cellosolve acetate, benzene, toluene, xylene,
Hydrocarbons such as hexane, methanol, ethanol, butanol, diacetone alcohol, isopropanol, secondary butanol, alcohols such as tertiary butanol, methylene chloride, chlorides such as dichloroethane, diethyl ether, ethers such as tetrahydrofuran, Examples thereof include aprotic polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone and the like, and a mixture of two or more kinds thereof.

The resin solid content at the time of polymerization is 5 to 95% by weight, preferably 10 to 80% by weight. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide and the like. The addition amount of the polymerization initiator is 0.001 to 10% by weight with respect to the radically polymerizable unsaturated monomer. Also,
Polymerization temperature is 10 to 160 ° C, preferably 30 to 140 ° C
Is.

The acrylic modified urethane resin composition of the present invention may be blended with various crosslinking agents and, if necessary, other resins to obtain a crosslinked coating film in order to further improve mechanical strength, chemical resistance and the like. it can. Examples of the cross-linking agent include polyisocyanate compounds, amino resins, epoxy compounds, silane compounds and metal chelate compounds. Examples of the polyisocyanate compound include p-phenylene diisocyanate, naphthalene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, lysine diisocyanate, and the like. Examples thereof include monomers, water adducts, and low molecular weight polyol adducts thereof.

As the amino resin, melamine, benzoguanamine, urea or the like can be used. Examples of the epoxy compound include bisphenol A type epoxy resin. Further, examples of the silane compound include acetoxysilane, alkoxysilane, ketoxime silane, aminosilane, and aminoxysilane. Examples of the metal chelate compound include alkoxides such as Ti, Zr, and Al, acetylacetonate, and acylate.

The other resin used in combination may be a known resin which is usually used for coating materials, as long as it has a certain degree of compatibility with the acrylic modified urethane resin composition.
Such polymers include acrylic resins, polyesters,
Examples thereof include polyurethane, polyether, polyamide, polycarbonate, polyvinyl chloride, phenol resin, alkyd resin and the like. The blending ratio of the resin and the acrylic modified urethane resin is preferably in the range of 90/10 to 0/100 in terms of other resin / acrylic modified urethane resin weight ratio. When the blend ratio is 90/10 or more, the effect of the acrylic modified urethane resin composition is poor.

The amount of the crosslinking agent added is preferably about 1 to 2 times the amount of the reactive functional groups in the crosslinking agent with respect to the amount of the hydroxyl groups contained in the acrylic modified urethane resin composition of the present invention. The formation of the crosslinked coating film is performed by applying a mixture containing a crosslinking agent and heating the mixture at 50 to 200 ° C for several hours to several seconds. At this time, a catalyst suitable for each reaction system may be added to the system in order to accelerate the crosslinking reaction. The catalyst used may be a commonly used catalyst. For example, when a polyisocyanate compound is used, a tertiary amine, an organic tin compound, or an epoxy compound is used.
Examples of silane compounds, such as primary amines and phenols, include organic acids and organic tin compounds.

Additives such as a filler, a reinforcing agent, a plasticizer, a stabilizer, a flame retardant, a release agent and a mildew proofing agent can be added to the acrylic modified urethane resin composition of the present invention as required. . Examples of fillers and reinforcing agents are carbon black, aluminum hydroxide, calcium carbonate, titanium oxide, silica, glass, bone powder, wood powder, fiber flakes, etc., plasticizers such as dibutyl phthalate, dioctyl phthalate, and stabilizers. Antioxidants, UV absorbers, light stabilizers, etc., chloroalkyl phosphate, dimethylmethylphosphonate ammonium polyphosphate organic bromine compounds, etc. as flame retardants, wax, soaps, silicone oil, etc. as mold release agents, and anti-mold agents. Is pentachlorophenol,
Pentachlorophenol laurate, bis (tri-n-
Butyltin) oxide and the like.

[0030]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples unless it exceeds the essential requirements. In the following, "part" means "part by weight". <Evaluation Items and Measuring Method> (1) The calculated values from the charged amount of hydroxyl value are shown in the table. (2) Viscosity E-type viscometer EHD-R type (manufactured by Tokimec Co., Ltd.) was used for measurement. Measurement temperature is 25 ℃, sample amount is 1.5m
1, a standard rotor (1 ° 34 ') was used. (3) Prepare a THF solution containing a resin having a molecular weight of 0.2%, and use a GPC device HL.
C-8020 (manufactured by Tosoh Corporation, column: G3000H)
XL, G4000HXL, G6000HXL), and the weight average molecular weight converted to standard polystyrene was calculated.

(4) Mitec (registered trademark) NY710A (H
10 parts of MDI TMP adduct, resin solid content of 75%, ethyl acetate solution, NCO 13.1%, manufactured by Mitsubishi Chemical Co., Ltd., based on 100 parts of acrylic modified urethane resin solid content, PMMA, acrylonitrile-butadiene -Styrene copolymer (ABS), PS, polyvinyl chloride molded plate (thickness 2 mm) was applied to a dry film thickness of about 50 μm and cured at 80 ° C. for 10 hours. After cutting, an adhesive tape “Cellotape” (trade name) manufactured by Nichiban Co., Ltd. was applied, and the test pieces were vigorously peeled off at 90 ° and evaluated by the number of remaining test pieces. ⊚: 100 remaining test pieces ○: 80-100 remaining test pieces Δ: 50-80 remaining test pieces ×: 50 or less remaining test pieces (5) Mechanical Strength According to JIS K6301, a tensile tester (Tensilon UTM-III-100 manufactured by Orientec Co., Ltd.) was used.
It was measured under the conditions of a pulling speed of 50 mm / min, a temperature of 23 ° C. and a relative humidity of 55%.

(6) Weather resistance Xenon weather ometer (Ci3 manufactured by Atlas Co., Ltd.)
5AW) black panel temperature 63 ° C, humidity 83%
The changes in coating film strength after irradiation with RH for 1000 hours were compared. (7) Chemical resistance According to JIS K5400, the alkali resistance, acid resistance and oil resistance of the coating film were evaluated. A 5% sodium hydroxide solution was used for alkali resistance and a 5% acetic acid solution was used for acid resistance. After immersion for 2 hours at a temperature of 50 ° C., the state of the coating film after washing with water and drying was judged from the appearance. Oil resistance is JIS K540
Using the test volatile oil Nos. 1 and 3 defined in 0.7, the state of the coating film after immersion at a temperature of 20 ° C. for 72 hours was judged from the appearance. ◎: No change in appearance ○: Degraded coating film surface △: Part of coating film eluted ×: Significant portion eluted

(8) Stain resistance Carbon black MA-100 (manufactured by Mitsubishi Chemical Co., Ltd.) is used as a pollutant, which is attached to gauze and lightly rubbed on the coating film. After leaving it in a thermostatic chamber at 20 ° C. and 75% RH for 24 hours, it is washed with running water. The degree of contamination of the coating film was visually determined and the result was displayed as follows. ◯: Good Δ: Slight stains remain ×: Slight stains remain XX: Peeling of coating film

(9) Solubility in organic solvent A coating film applied to give a dry film thickness of 100 μm was dipped in methyl ethyl ketone at a resin solid content of 20% by weight,
The heating residue when heated at 75 ° C. for 10 hours was measured.
For Comparative Example 2, Mitec (registered trademark) NY710A (HMDI TMP) was used as a polyisocyanate curing agent.
Additive, resin solid content 75%, ethyl acetate solution, NCO1
It was evaluated that 3.1% of Mitsubishi Chemical Co., Ltd. was added to 10 parts of 100 parts of the main agent.

Example 1 4 equipped with a stirrer, reflux condenser, dropping funnel and thermometer
Isophorone diisocyanate 31.4 in a two-necked flask
Parts were charged, heated to 90 ° C. and melted while stirring (Plaxel CD220, hydroxyl value 56.1 KOHmg / g, Daicel Chemical Industries Ltd.)
(Made by Nippon Oil & Fats Co., Ltd.), and 128.4 parts of glycerin monomethacrylate (manufactured by NOF CORPORATION) and 0.02 part of methylhydroquinone were added dropwise in about 1 hour. After keeping the internal temperature at 90 ° C. and reacting for 4 hours, 208.9 parts of methyl ethyl ketone was added, and the mixture was stirred at 60 ° C. for 1 hour for dilution. Next, a solution of 8.7 parts of isophoronediamine and 52.2 parts of isopropanol was added dropwise with stirring for about 1 hour. Further, 3.3 parts of dibutylamine was added to block the end.
Subsequently, 24.6 parts of 1,4-cyclohexanedimethanol monoacrylate and 149.5 parts of methyl methacrylate were charged and heated to 70 ° C. under a nitrogen stream to obtain 5.2 parts of azobisisobitylonitrile (AIBN). The mixture was divided and added at 1 hour intervals, and the reaction was continued for 10 hours. The obtained acrylic modified urethane resin composition has a resin solid content of 35% and a viscosity of 5
It was 00 mPa · s and the weight average molecular weight was 46,000.
The production results and evaluation results are shown in Tables 1 and 2.

Examples 2 to 5 and Comparative Example 1 A modified urethane resin composition was obtained using the same reactor, reaction conditions, raw materials and charging amounts shown in Table 1 as in Example 1. The results are shown in Table 2.
It was shown to. Comparative Example 2 4 equipped with stirrer, reflux condenser, dropping funnel, thermometer
In a two-necked flask, 24.6 parts of 1,4-cyclohexanedimethanol monoacrylate and 32 methyl methacrylate
After charging 5.4 parts and 650 parts of methyl ethyl ketone, the mixture was heated to 70 ° C. under a nitrogen stream, 10.5 parts of AIBN was divided into 3 portions and added at 1 hour intervals, and reacted for 10 hours. The obtained acrylic resin has a resin solid content of 35% and a viscosity of 2000 mPa.
and the weight average molecular weight was 35,000.

Comparative Example 3 4 equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer
Isophorone diisocyanate 72.1 in a two-necked flask
Parts were charged, heated to 90 ° C. and melted while stirring (Plaxel CD220, hydroxyl value 56.1 KOHmg / g, Daicel Chemical Industries Ltd.)
(Manufactured by Mitsui Chemicals Co., Ltd.) Inner temperature is 90 ° C
After reacting for 4 hours, the methyl ethyl ketone 480
Parts were added, and the mixture was stirred at 60 ° C. for 1 hour for dilution. Then, with stirring, 25.1 parts of isophoronediamine and 1 of isopropanol
20 parts of the solution was added dropwise in about 1 hour. Further, 7.6 parts of dibutylamine was added to block the end. The resulting urethane resin has a resin solid content of 40% and a viscosity of 1750 mPa.
and the weight average molecular weight was 52,000.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

The acrylic-modified urethane resin composition obtained by the present invention has adhesiveness to various plastic materials,
It has excellent weather resistance, mechanical strength, chemical resistance, and stain resistance, and is soluble in organic solvents, so it can be used as a binder for printing inks and decoration for various synthetic resin moldings and for surface protection. It is extremely useful as a paint resin, adhesive, and coating agent.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J027 AG01 AG02 AG22 AG33 BA03                       BA08 CD08 CD09                 4J034 BA07 BA08 CA01 CA11 DA01                       DB03 DB07 DC50 DG02 DH02                       DM01 DP19 FA02 FB01 FC01                       FD04 HA07 RA07 RA08

Claims (3)

[Claims] 1. A radical containing 1 to 99% by weight of a urethane resin obtained by reacting at least an organic diisocyanate, a high molecular weight polyol and a chain extender, and 1,4-cyclohexanedimethanol mono (meth) acrylate as essential components. An acrylic-modified urethane resin composition obtained by copolymerizing 99-1% by weight of a polymerizable unsaturated monomer. 2. The acrylic modified urethane resin composition according to claim 1, which is soluble in an organic solvent. 3. Reaction of an organic diisocyanate, a high molecular weight polyol, a radical-polymerizable double bond-containing compound having at least one active hydrogen and at least one radical-polymerizable double bond in the same molecule, and a chain extender. At the very least, a urethane resin containing 1 to 200 μeq / g of a radical polymerizable double bond and a radical polymerizable double bond having a weight average molecular weight of 10,000 to 200,000 is used.
To 99% by weight and 99 to 1% by weight of a radical-polymerizable unsaturated monomer containing 1,4-cyclohexanedimethanol mono (meth) acrylate as an essential component are radically reacted. A method for producing a composition.