JP3065266B2 - Method for producing resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a resin composition which is cured by active energy rays such as ultraviolet rays.

[0002]

2. Description of the Related Art In recent years, active energy ray-curable paints which are cured by irradiation with active energy rays such as ultraviolet rays have been widely used in place of organic solvent-based paints due to environmental pollution problems and energy saving. This is because it contains a resin and a monomer that can be cured by irradiation with active energy rays such as ultraviolet rays, and has an advantage that the solvent does not volatilize during the formation of a coating film because the monomer also functions as a solvent. An oligomer having an acrylic double bond at the molecular terminal such as polyester acrylate, urethane acrylate, epoxy acrylate, or a styrene-based or acrylic-based monomer is used as the resin having an active energy ray-curing property.

[0003] Among them, urethane acrylic (urethane acrylate) resin has a good balance of physical properties, and a coating composition using the resin is used for coating of decorative boards, gloss for paper, paint for woodwork, hard coat, adhesive, Widely used for applications such as resist materials. Such a urethane acrylic (urethane acrylate) resin is generally obtained by reacting a polyvalent isocyanate component, a polyhydric alcohol component, an acid diol component, a hydroxyl group-containing (meth) acrylate component, and the like. Various characteristics are ensured by adjusting the reaction order and the reaction ratio of the above.

For example, Japanese Patent Publication No. 7-80989 discloses, for the purpose of transparency, adhesion, dispersibility and the like of a cured film,
A process for producing a terminal isocyanate urethane oligomer, a process for producing a carboxyl group-containing terminal isocyanate urethane oligomer, and a process for obtaining a carboxyl group-containing urethane (meth) acrylate is disclosed, and Japanese Patent Publication No. 7-80990. In the gazette,
(4) a step of producing a terminal isocyanate diol adduct compound, a step of producing a carboxyl group-containing terminal hydroxyl urethane oligomer, a step of producing a carboxyl group-containing terminal isocyanate urethane oligomer, and a step of obtaining a carboxyl group-containing urethane (meth) acrylate
A manufacturing method comprising steps is disclosed.

[0005]

However, in the disclosed method as described above, it is difficult to improve the adhesion to the substrate while maintaining the film strength such as elongation and tensile strength. It is also difficult to improve the swelling and releasability (use of a resist material), and further improvement is desired.

[0006]

The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, (A) polyvalent isocyanate, (B) polyhydric alcohol, (C) acid diol and (D) In producing a resin composition obtained by reacting a hydroxyl group-containing (meth) acrylate, the ratio of the isocyanate group in (A) to the hydroxyl group in (C) is more than 1 in the molar ratio of (A) to (A). Step (I) in which C) is reacted to obtain a terminal isocyanate diol adduct compound (a), (B) for the isocyanate group in (a)
(A) and (B) in a molar ratio of less than 1 to obtain carboxyl group-containing terminal isocyanurethane oligomer (b) (II), (D) relative to isocyanate group in (b) The resin composition obtained by the production method comprising the step (III) of reacting (b) and (D) at a molar ratio such that the proportion of hydroxyl groups in the compound is 1 or more to obtain a carboxyl group-containing urethane (meth) acrylate is Excellent in adhesiveness to a substrate and swelling and peeling property (decomposition / solubility in an alkali aqueous solution, or alkali solubility) in an alkali aqueous solution while maintaining film strength such as elongation and tensile strength. Have excellent storage stability and transparency, and have found that a good film can be obtained without forming a surface tack on the formed film, thereby completing the present invention.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
Examples of the (A) polyvalent isocyanate component used in the present invention include aromatic, aliphatic, cycloaliphatic, and alicyclic polyisocyanates or a mixture thereof. Or tolylene diisocyanate such as 2,6-tolylene diisocyanate (T
DI), and mixtures thereof, diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H-MDI), polyphenylmethane polyisocyanate (crude MDI), modified diphenylmethane diisocyanate (modified MDI), hydrogenated xylylene diisocyanate ( H-XDI), xylylene diisocyanate (XDI), aromatic polyisocyanates such as hexamethylene diisocyanate (HMDI), trimethylhexamethylene diisocyanate (TMXDI), trimer compounds of these polyisocyanates, and isophorone diisocyanate (IPDI). Aliphatic polyisocyanate, norbornene diisocyanate (NBD
I) and reaction products of these polyisocyanates and polyols, and 2,4-tolylene diisocyanate, isophorone diisocyanate (IPDI), and norbornene diisocyanate (NBDI) are preferably used.

The polyhydric alcohol component (B) includes ethylene glycol, 1,2- or 1,3-propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, 1,3 -Or 1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, neopentyl glycol,
2-methylpentanediol, cyclohexanedimethanol, hydrogenated bisphenol A, polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, polycaprolactone, trimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythol, Polypentaerythol, sorbitol, mannitol, glycerin, polyhydric alcohols such as polyglycerin and the polyhydric alcohol and maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid,
Examples include polyester polyols, caprolactone-modified polyols, polyolefin-based polyols, polycarbonate-based polyols, and polybutadiene-based polyols, which are reactants with polybasic acids such as isophthalic acid, and bifunctional polyols having a hydroxyl value of 35 to 560 mgKOH / g are preferable. Used for

The (C) acid diol component includes:
2,2-di (hydroxymethyl) propionic acid, 2,2
-Caprolactone-free adduct of di (hydroxymethyl) propionic acid, 2,2-di (hydroxymethyl) butyric acid, dimethylolheptanoic acid, tartaric acid having two carboxyl groups, and the like. (Hydroxymethyl) propionic acid and 2,2-di (hydroxymethyl) butyric acid are used. Further, as the (D) hydroxyl group-containing (meth) acrylate component, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, pentaerythritol triacrylate, 2-hydroxyethyl acryloyl phosphate, 4-hydroxybutyl acrylate, caprolactone-modified 2-hydroxyethyl acrylate, and the like, among which 2-hydroxyethyl acrylate, Pentaerythritol triacrylate and caprolactone-modified 2-hydroxyethyl acrylate are preferably used.

In the present invention, the above (A) to (D)
Is reacted in a specific method. That is, in producing the resin composition by reacting the above (A) to (D), the molar ratio of the isocyanate group in (A) to the hydroxyl group in (C) exceeds 1 with (A). Reacting (C) to obtain terminal isocyanate diol adduct compound (a) (I), (a)
(B) reacting (a) and (B) at a molar ratio of the hydroxyl group in (B) to the isocyanate group in the mixture of less than 1 to obtain a carboxyl group-containing isocyanate urethane oligomer (b); (I) in the step (III) of the step (III) of reacting (b) and (D) at a molar ratio such that the ratio of the hydroxyl group in (D) to the isocyanate group in the (I) is 1 or more to obtain a carboxyl group-containing urethane (meth) acrylate. ) ~
The target resin composition is obtained by sequentially performing (III).

More specifically, in the above step (I), the molar ratio of the isocyanate group in (A) to the hydroxyl group in (C) exceeds 1 (preferably from 1.2 to 2.0). 2) Charge (A) and (C) as shown
0 to 120 ° C (further 70 to 100 ° C) (If the reaction temperature is lower than 60 ° C, it is difficult to complete the reaction,
Conversely, if the temperature exceeds 120 ° C., gelation due to a side reaction is likely to occur, which is not preferable), and the reaction is carried out for about 1 to 12 hours (further, 2 to 8 hours) to obtain a terminal isocyanate diol adduct compound (a). is there. In the step (I), when the molar ratio of the isocyanate group in (A) to the hydroxyl group in (C) is 1 or less, a urethane oligomer having a terminal isocyanate cannot be obtained. Does not work effectively,
Curing by active energy rays is not sufficiently performed, and the cured film does not exhibit sufficient strength and hardness, so that the object of the present invention cannot be achieved.

In the following step (II), the obtained (a)
The molar ratio of the hydroxyl group in (B) to the isocyanate group in (a) is less than 1 (preferably 0.75 to 0.4
5) As described in (B), it is difficult to complete the reaction if the reaction temperature is lower than 60 to 120 ° C. (further 70 to 100 ° C.). It is not preferable because gelation occurs easily.)
The reaction is carried out for about 1 to 10 hours (further 2 to 8 hours) to obtain a carboxyl group-containing terminal isocyanurethane oligomer (b). In the step (II), when the molar ratio of the hydroxyl group in (B) to the isocyanate group in (a) exceeds 1, the terminal of the resulting carboxyl group-containing urethane oligomer becomes a hydroxyl group and the desired terminal of the carboxyl group-containing is obtained. No isocyanate urethane oligomer can be obtained.

In the last step (III), the obtained (b)
(D) was charged so that the molar ratio of the hydroxyl group in (D) to the isocyanate group in (b) was 1 or more (further 1.01 to 1.2), ~ 80
C.), and the reaction is carried out for about 1 to 12 hours (further 3 to 10 hours) to obtain the carboxyl group-containing urethane (meth) acrylate composition which is the resin composition of the present invention. Also in (III), when the molar ratio of the hydroxyl group in (D) to the isocyanate group in (b) is less than 1, the isocyanate group remains in the obtained carboxyl group-containing urethane (meth) acrylate composition. , Storage stability is reduced, and the object of the present invention cannot be achieved.

In the above steps (I) to (III), it is preferable to add about 50 to 1200 ppm of quinones such as hydroquinone, hydroquinone monomethyl ether and benzoquinone, phenothiazine and copper salts as stabilizers. In (I), it is also preferable to use an inert solvent and an organic solvent such as ethyl acetate, methoxypropyl acetate, ethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate which are inert. The resin composition obtained by the production method of the present invention as described above is useful as an active energy ray-curable resin composition. Hereinafter, such an active energy ray-curable resin composition will be described.

Such a resin composition generally contains a photopolymerization initiator in addition to the curable resin composition of the present invention and, if necessary, an ethylenically unsaturated monomer.
Examples of such a photopolymerization initiator include cobalt octenoate, cobalt naphthenate, manganese octenoate, manganese naphthenate, methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, and t-butyl peroxide. Benzoate, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, anthraquinone, naphthoquinone, hibaroin ethyl ether, benzyl ketal, 1,1-dichloroacetophenone, pt
-Butyldichloroacetophenone, 2-chlorothioxanthone, 2,2-diethoxyacetophenone, Michler's ketone, 2,2-dichloro-4-phenoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, benzophenone, 2-methylthioxanthone, phenyl Glyoxylate, α-hydroxyisobutylphenone, dibenzosparone, benzophenoneamines (N-methyldiethanolamine, triethylamine, etc.), benzyldiphenyldisulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, dibenzyl, diacetyl, acetophenone, benzyl Dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- Such emission methylbenzoyl formate and the like.

The ethylenically unsaturated monomer is not particularly limited as long as it has an ethylenically unsaturated bond. Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (Meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2 −
Dicyclopentenoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, tetrahydrofurifuri (Meth) acrylate, carbitol acrylate, benzyl acrylate, allyl acrylate, phenoxyethyl acrylate, styrene,
Vinyltoluene, chlorostyrene, α-methylstyrene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, acryloxyethyl phosphate, 2-vinylpyridine, 2-ethylhexyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl Acrylate, ethyl carbitol acrylate, polypropylene glycol diacrylate, polyethylene glycol (# 200, # 400, # 600) diacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl succinic acid, 1,6-hexane Diol diacrylate, trimethylolpropane triacrylate, EO (ethylene oxide) -modified trimethylolpropane triacrylate, methyl triglyco Le, acryloyl morpholine, 1,9-nonanediol diacrylate, 2-n-
Butyl-2-ethyl-1,3-propanediol diacrylate and the like, among which 1,9-nonanediol diacrylate, 2-n-butyl-2-ethyl-1,3
-Propanediol diacrylate and EO (ethylene oxide) -modified trimethylolpropane triacrylate are preferably used.

The amount of the photopolymerization initiator and the ethylenically unsaturated monomer in the present invention is not particularly limited, but the amount of the photopolymerization initiator may be 1 to 1 with respect to the entire active energy ray-curable resin composition. It is about 10% by weight, and the compounding ratio of the curable resin composition to the ethylenically unsaturated monomer may be 95/5 to 15/85 in the compounding ratio of the curable resin composition and the ethylenically unsaturated monomer. Preferably
More preferably, it is 90/10 to 30/70, and when the compounding weight ratio of the curable resin composition exceeds the above range, the viscosity of the compounding composition becomes high and the workability is remarkably reduced when used for coating or the like, Conversely, if the weight ratio of the ethylenically unsaturated monomer exceeds the above weight ratio, the toughness of the resulting film tends to decrease, and the scratch resistance tends to decrease, which is not preferable.

The active energy ray-curable resin composition may be added with an organic solvent, if necessary, such as a ketone solvent such as acetone, methyl ethyl ketone and cyclohexanone, and methyl acetate. ,
Ethyl acetate, butyl acetate, ethyl lactate, methoxyethyl acetate, propylene glycol monomethyl ether acetate, ester solvents such as ethylene glycol diacetate, diethyl ether, ethylene glycol dimethyl ether, ether solvents such as dioxane, toluene,
Examples include aromatic solvents such as xylene, aliphatic solvents such as pentane and hexane, halogen solvents such as methylene chloride, chlorobenzene and chloroform, and alcohol solvents such as isopropyl alcohol and butanol.

Further, when used as a paint, pigments, fillers, leveling agents, thermoplastic resins and the like are often added as additives. Examples of the pigment include titanium white, cyanine blue, cream yellow, watching red, red bengal, carbon black, and aniline black.

As the thermoplastic resin, cellulose acetate butyrate, nitrocellulose, vinyl chloride resin,
Vinyl acetate resin, acrylic resin and their copolymers,
Butylated melamine, butylated urea and the like can be mentioned. Also, it can be used in combination with a wax type unsaturated polyester resin. Other additives include phosphoric acid, tartaric acid, phosphorous acid, fats and oils, silicone oil, surfactants and the like.

As a method of forming a cured film from such a resin composition, a coating film applied to an object to be coated is irradiated with active energy rays to be cured. As the energy ray, far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, X rays
Electron beams, proton beams, neutron beams, etc. can be used in addition to electromagnetic waves such as X-rays and γ-rays. However, film formation (curing)
The curing method by ultraviolet irradiation is advantageous from the viewpoint of speed, availability of a radiation irradiation apparatus, and price. Ultraviolet rays as used in the present invention is mainly composed of light in the wavelength range of 150 to 450 nm, and is irradiated using a chemical lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, or the like.

As a coating method, a known method such as a curtain coater, a roll coater, a flow rotor, spraying, dipping and the like can be adopted. Although the thickness of the coating film cannot be unconditionally determined depending on the object to be coated or the application, it can usually be suitably selected from the range of 5 to 200 μm. Further, as the object to be coated, vinyl chloride resin, polyethylene terephthalate (PET), polymethacrylate,
From plastics such as polycarbonate and nylon (polyamide), wood, metal plate, metal oxide film, glass,
It can be widely used in ceramics, paper and concrete. The plastics, wood, paper, metal plate and the like coated with the resin composition of the present invention are useful for various building materials, furniture, printing paper, can products, household electric appliances and the like.

[0023]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, “parts” means on a weight basis unless otherwise specified. Example 1 [Step (I)] 6.0 mol (23.14) of (A) isophorone diisocyanate (IPDI) was placed in a 2 liter flask.
Parts) and (C) 3,0 mol of dimethylolbutanoic acid (7.
7 parts) so that the ratio (molar ratio) of the isocyanate groups in (A) to the hydroxyl groups in (C) is 2.0, and 30.0 parts of ethyl acetate are further charged. (About 78 ° C.) for about 6 hours to obtain a terminal isocyanate diol adduct compound (a).

[Step (II)] Then, 2.0 mol (35.09 parts) of (B) polyester polyol (a saturated polyester diol having a molar ratio of adipic acid / ethylene glycol / diethylene glycol = 1 / 0.5 / 0.5) ) Was charged so that the ratio (molar ratio) of the hydroxyl group in (B) to the isocyanate group in (a) was 0.67, and the reaction was further continued for about 11 hours to obtain a carboxyl group-containing terminal isocyanate urethane oligomer (b) ) Got.

[Step (III)] Thereafter, the mixture is cooled to about 60 ° C. to give (D) 2-hydroxyethyl acrylate 2.0
The mole (4.0 parts) was charged so that the ratio (molar ratio) of the hydroxyl group in (D) to the isocyanate group in (c) was 1.02, and further 0.01% by weight of monomethyl ether hydroquinone (system) 50-70 in addition)
After stirring for about 6 hours at a temperature of
-Butyltin was added in an amount of 0.01 part based on 100 parts of the total amount of (A) to (D), and the reaction was continued for 6 hours or more. When the residual isocyanate group became 0.1% by weight, the reaction was started. After finishing, the resin composition of the present invention, a carboxyl group-containing urethane (meth) acrylate (viscosity: 57000 cp)
s / 20 ° C, acid value; 27.7 KOHmg / g).
The storage stability of the resin composition obtained above was evaluated in the following manner.

(Storage stability) 300 g of the obtained resin composition was placed in a 500 ml mayonnaise bottle, left in a hot air drier at 60 ° C. for 10 days, and the container was inverted to generate a gel. The presence or absence was visually observed and evaluated as follows. ○ --- No occurrence of gel-like substance was observed. × --- Generation of gel-like substance was observed. Next, 1-hydroxycyclohexyl phenyl ketone (Ciba Geigy) was used as a photopolymerization initiator in 100 parts of the obtained resin composition. After mixing 4 parts of “IRGACURE 184” (manufactured by K.K.) into an active energy ray-curable resin composition, the strength, Young's modulus, adhesion, surface tack and alkali solubility of the cured film were evaluated in the following manner.

(Strength, Young's modulus)
A gap of 125 μm on a PET film having a thickness of 00 μm.
Coated with a doctor blade of μm, left in a hot air dryer at 60 ° C. for 5 minutes, and then dried at a line speed of 5 m / min.
After passing once under an 80 W / cm mercury lamp installed at a height of 0 cm (integrated light amount: 161 mj / cm ² ) to form a film (thickness after curing is 60 μm), PET
Strip the coating film from the film into a strip shape (15 mm x 150 mm) and use a tensile tester ("Autograph AG-100" manufactured by Shimadzu Corporation, tensile speed 10 mm / min) at 20 ° C and 65% RH. Strength at break (kg / cm ² )
Was measured. At the same time, the Young's modulus (kg
/ Cm ² ).

(Adhesion) The above resin composition was coated on a galvanized steel plate (6 cm × 12 cm) with a doctor blade having a gap of 50 μm, and dried in a 60 ° C. hot air drier.
After leaving for 20 minutes, 20 cm at a line speed of 5 m / min
After passing once under an 80 W / cm mercury lamp (integrated light amount: 161 mj / cm ² ) set at a height of 2,000 K / cm and 65% RH under JIS K54.
100 on the coating film according to
After making cell / cm ² squares, applying cellophane tape from above and rolling it sufficiently with an eraser, two minutes later, the cellophane tape was peeled off at once, and the number of cells left on the glass plate and the status of the remaining cells Was observed and evaluated as follows. −−−− The number of remaining cells was 91 / cm ² or more. △ −−− The number of remaining cells was 90 to 50 cells / cm ² × −−− The number of remaining cells was 49 cells / cm ² or less

(Surface Tack) The above resin composition was coated on a glass plate (6 cm × 12 cm) with a doctor blade with a gap of 50 μm, left in a 60 ° C. hot air drier for 5 minutes, and then 5 m / min. After passing once under an 80 W / cm mercury lamp installed at a height of 20 cm at a line speed of (integrated light amount: 161 mj / cm ² ), a cured film is formed, and then at 20 ° C. and 65% RH. The surface of the coating film was examined for the presence or absence of tack by a finger touch and evaluated as follows. ○ −−− No surface tack is observed × −−− Surface tack is observed

(Alkali-soluble) The above cured film (including the glass plate) was placed in a 500 ml beaker at 50 ° C.
Immersed in a 5% aqueous sodium hydroxide solution (400 ml), and the aqueous solution was forcibly stirred with a stirrer to measure the time until the cured film was completely removed from the glass plate.
The evaluation was as follows. ◎ −−− less than 30 seconds ○ −−− 30 seconds or more and less than 1 minute Δ −−− 1 minute or more and less than 3 minutes × −−− 3 minutes or more

Example 2 In Example 1, 2.0 mol (12.52 parts) of pentaerythritol triacrylate was used instead of 2.0 mol (4.0 parts) of (D) 2-hydroxyethyl acrylate.
Was prepared in the same manner except that the ratio (molar ratio) of the hydroxyl group in (D) to the isocyanate group in (b) was 1.02, and the resin composition of the present invention (viscosity: 970)
00 cps / 20 ° C., acid value; 24.9 KOHmg / g)
And evaluated similarly.

Example 3 In Example 1, dimethylolbutanoic acid was replaced by 3.0 mol (6.76) in place of (C) dimethylolpropionic acid.
Part), the resin composition of the present invention (viscosity: 49000 cp) was prepared in the same manner except that the ratio (molar ratio) of the isocyanate group in (A) to the hydroxyl group in (C) was changed to 2.0.
s / 20 ° C., acid value; 27.2 KOH mg / g),
Evaluation was performed similarly.

Comparative Example 1 In the same manner as in Example 1 except that the ratio (molar ratio) of the isocyanate group in (A) to the hydroxyl group in (C) was changed to 0.67 in the step (I) of Example 1. Go to the resin composition (viscosity; 20000 cps / 20 ° C., acid value; 27.
8KOHmg / g) was obtained and evaluated in the same manner.

Comparative Example 2 In the same manner as in Example 1 except that the ratio (molar ratio) of the hydroxyl group in (B) to the isocyanate group in (a) was changed to 1.33 in the step (II) of Example 1. Go to the resin composition (viscosity; 53000 cps / 20 ° C., acid value; 27.
7KOH mg / g) and evaluated in the same manner.

Comparative Example 3 In the same manner as in Example 1 except that the ratio (molar ratio) of the hydroxyl group in (D) to the isocyanate group in (c) was changed to 0.5 in Step (III) of Example 1. Then, the resin composition (viscosity; 55000 cps / 20 ° C., acid value; 29.0)
KOHmg / g) was obtained and evaluated in the same manner. Table 1 shows the evaluation results of the examples and the comparative examples.

[0036]

[Table 1] Storage stability Strength Young's modulus Adhesion Surface tack Alkali solubility (kg / cm ² ) (kg / cm ² ) Example 1 ○ 120 110 ○ ○ ○ 〃 2 ○ 280 3200 ○ ○ ○ ○ 3 ○ 140 100 ○ ○ ◎ Comparative Example 1 ○ 10 5 △ × ○ △ 2 ○ 50 30 × × × △ 3 × 30 50 △ × ○

[0037]

As described above, the resin composition of the present invention is obtained by reacting (A) to (D) in a specific order and ratio as described above. , Storage stability, transparency, etc., and when the active energy ray-curable resin composition is used, the cured film has an excellent balance of hardness, elongation, strength, etc. Excellent decomposition / solubility to aqueous solution), and the formed film is a good film without surface tack, and various building materials such as plastics, wood, paper, glass, ceramics, metal plates, furniture, printing paper, cans It is very useful as a coating for products, household electric appliances, electronic parts, etc. and as a protective film for primary processing.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08G 18 / 10,18 / 67 C08F 299/06

Claims (2)

(57) [Claims] In producing a resin composition obtained by reacting (A) a polyisocyanate, (B) a polyhydric alcohol, (C) an acid diol, and (D) a hydroxyl group-containing (meth) acrylate, (C) Reacting (A) and (C) at a molar ratio where the ratio of isocyanate groups in (A) to hydroxyl groups in (A) exceeds 1, to obtain terminal isocyanate diol adduct compound (a) (I), (a) (B) reacting (a) and (B) at a molar ratio of the hydroxyl group in (B) to the isocyanate group in the mixture of less than 1 to obtain a carboxyl group-containing isocyanate urethane oligomer (b); (B) in a molar ratio such that the ratio of the hydroxyl groups in (D) to the isocyanate groups in ()) is 1 or more.
And (D) to obtain a carboxyl group-containing urethane (meth) acrylate to obtain a resin composition. 2. The method for producing a resin composition according to claim 1, wherein the resin composition is a resin composition that is cured by an active energy ray.