JP2001131496A - Curable resin composition for protection of transfer film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition for protection of a transfer film capable of protecting the film transferred to a plastic molding in a good state. SOLUTION: In a resin composition of which a coating film made for protection of a transfer film formed on an article, the curable resin composition for protection of the transfer film comprises a polymer which is obtained by copolymerizing (a) a radical polymerizable monomer having a hydroxyl group modified by a caprolactone monomer of 1<= to <=20 mole in terms of an average mole number, and (b) another radical polymerizable monomer copolymerizable with the above (a) radical polymerizable monomer, and an isocyanate prepolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a protective curable resin composition suitable for protecting a transfer film transferred and printed on an article such as a plastics molded article.

[0002]

BACKGROUND ART In recent years, various plastics molded products,
For example, in various automobile parts such as ornaments, armrests, and emblems, patterns, characters, symbols, or a combination thereof are transferred (hereinafter, referred to as transfer patterns) on a plastic molded product. Hot stamp transfer printing, in which a film or metal foil on which such a transfer pattern is drawn by applying heat, or injection molding in which a transfer pattern is formed by an in-mold transfer molding method, has been widely used. .

Here, the in-mold transfer molding method is
This is a molding simultaneous transfer method that simultaneously performs molding by plastic injection molding and transfer printing.The foil or film to be transferred is sent into a molding die, and at the same time as molding, transfer printing is performed using the heat and pressure. It is a method of construction.

A transfer film of a transfer design on an article to which a foil or a design film obtained by the transfer printing method is transferred has a poor durability against external mechanical stimuli, and thus is easily scratched or peeled off. There was a disadvantage of doing so. In order to remedy this drawback, attempts have been made to apply a protective coating of acrylic urethane resin to the transfer film transferred and printed on the surface of the article.However, a soft protective film is formed on the transfer printing surface to form a printed surface. In the case where protection is performed, there are problems such as a decrease in durability against a solvent and a decrease in adhesion to a transfer printing film and a base molded product.

Further, when a hard protective film is formed on the transfer printing surface to protect the printing surface, there is a problem that the protective coating film is easily cracked when handling the article coated with the protective coating. . Furthermore, although excellent weather resistance is generally required for automotive exterior parts, at present, there is no protective film suitable for protective coating of a transfer film and imparting excellent weather resistance. For this reason, it has been extremely difficult to adopt the transfer-printed article as a vehicle exterior part.

[0006]

DISCLOSURE OF THE INVENTION In order to solve the above-mentioned problems, the present invention has an advantage that the adhesion strength and the mechanical strength to an article and a transfer film without adversely affecting the transfer film transferred on the article. It is an object to improve the weather resistance of the protective coating film itself at the same time as improving the protective film. In order to solve this problem, a transfer film transferred and printed by a hot stamp transfer printing method or an in-mold transfer molding method, a curable resin composition comprising a resin having a hydroxyl group composed of a specific component and an isocyanate prepolymer It is characterized by being covered with and protected by.

[0007]

Means for Solving the Problems In order to solve the above-mentioned problems, a first invention is directed to a resin composition for forming a coating film for protecting a transfer film formed on an article, the average number of moles of the resin composition. A radical polymerizable monomer (a) having a hydroxyl group modified by at least 1 mol and not more than 20 mol of a caprolactone monomer, and a radical copolymerizable with a radical polymerizable monomer having a hydroxyl group modified by the caprolactone monomer Polymerizable monomer (b)
And a curable resin composition for protecting a transfer film, which comprises a polymer obtained by copolymerizing the above and a isocyanate prepolymer.

According to a second aspect of the present invention, a polymer obtained by polymerizing the radically polymerizable monomer (b) according to the first aspect has a glass transition temperature of 50 ° C. or more. Another object of the present invention is to provide a curable resin composition for protecting a transfer film.

According to a third aspect of the present invention, there is provided a protective film for protecting a transfer film according to the first or second aspect, which has a hydroxyl value of 5 to 30 mgKOH / g. The present invention provides a conductive resin composition.

[0010] In order to solve the above-mentioned problem, a fourth invention provides a method according to any one of the first to third aspects, wherein the weight average molecular weight is 10,000 to 50,000 in terms of styrene. An object of the present invention is to provide a curable resin composition for protecting a transfer film.

According to a fifth aspect of the present invention, there is provided a liquid crystal display device according to any one of the first to third aspects, wherein the radical polymerizable monomer having an ultraviolet absorbing property is 0.1.
It is intended to provide a curable resin composition for protecting a transfer film, wherein the curable resin composition is copolymerized at 5 to 20.0% by weight.

[0012] In order to solve the above-mentioned problems, a sixth invention according to any one of claims 1 to 5, wherein 0.1 to 5.0% by weight of hindered amine-based light-stable in a solid content. An object of the present invention is to provide a curable resin composition for protecting a transfer film, which comprises an agent.

According to a seventh aspect of the present invention, the transfer film is coated with the protective curable resin composition according to any one of the first to sixth aspects. An article characterized by the following is provided.

In order to solve the above-mentioned problem, an eighth aspect of the present invention provides a method for protecting the transfer film by covering the transfer film with the protective curable resin composition according to any one of claims 1 to 6. And a method for protecting the transfer film.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a curable resin composition used for protecting a transfer film transferred and printed by a hot stamp transfer printing method or an in-mold transfer molding method. A resin having a certain polyester component and having a hydroxyl group as a main chain component, which is a polymer of a radical polymerizable monomer such as acrylate, methacrylate or styrene, is used.

Examples of the radically polymerizable monomer having a hydroxyl group modified with the caprolactone monomer as the component (a) include 2-hydroxyethyl acrylate and 2-hydroxyethyl acrylate.
A compound obtained by ring-opening addition of epsilon caprolactone to a radical polymerizable monomer having a hydroxyl group such as hydroxyethyl methacrylate in the presence of a catalyst such as tin chloride can be used.

For example, FA-1, FA-2, FA-
3, FA-4, FA-5, FA-7.5, FA-10,
FA-20, FM-1, FM-2, FM-3, FM-
4, FM-5, FM-7.5, FM-10, FM-2
0 (the above-mentioned epsilon caprolactone modified hydroxyl group-containing radical polymerizable monomer manufactured by Daicel Chemical Co., Ltd.) and the like.

Further, the amount of the hydroxyl group-containing radical polymerizable monomer modified with the caprolactone monomer, which is modified with the caprolactone monomer, is preferably 1 to 20 mol per 1 mol of the monomer before modification. More preferably, it is 1.5 to 10 mol. When the amount is less than 1 mol, the transfer film covered with the protective film has poor scratch resistance and disadvantages such as cracks occurring between the article and the transfer film during assembly of the article.

If the amount is 20 mol or more, the effect of the present invention cannot be obtained, and some caprolactone components are not preferable because a problem occurs in storage stability of the resin due to crystallinity.

The component (b) is a monomer which can be radically copolymerized with the component (a), and examples thereof include the following radically polymerizable monomers.

As component (b), esters of acrylic acid or methacrylic acid, such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate C1 to C1 of acrylic acid or methacrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, etc.
18 alkyl esters, methoxybutyl acrylate,
Acrylic acid such as methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate, etc., or an alkoxyalkyl ester having 2 to 18 carbon atoms of methacrylic acid, acrylic such as allyl acrylate, allyl methacrylate C2-C8 alkenyl ester of acid or methacrylic acid, such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc. Acrylic acid or methacrylate such as hydroxyalkyl ester, allyloxyethyl acrylate, allyloxyethyl methacrylate Illustrate alkenyloxy alkyl esters having 3 to 18 carbon atoms Le acids.

Further, as the vinyl aromatic compound, for example, styrene, α-methylstyrene, vinyltoluene,
p-Chlorostyrene can be exemplified.

Examples of the polyolefin-based compound include butadiene, isoprene, and chloroprene. In addition, acrylonitrile, methacrylonitrile, methyl isopropenyl ketone, vinyl acetate, vinyl propionate, vinyl pivalate, acrylamide, N-methylol acrylamide, and N- Examples include methylol methacrylamide, N-methylol acrylamide butyl ether, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, allyl alcohol, and maleic acid.

Particularly, the monomer constituting the component (b) is
When only the component (b) is polymerized to obtain a polymer, the glass transition temperature is preferably 50 ° C. or higher. It is more preferably at least 80 ° C. If the temperature is lower than 50 ° C., the durability of the protective film to an organic solvent decreases, and the transfer film cannot be sufficiently protected, which is not preferable.

Although the glass transition temperature of the polymer generally has a wide range, the glass transition temperature of the component (b) in the present invention depends on the glass transition temperature when each monomer component is polymerized and the glass transition temperature in the copolymer. And the value obtained by the arithmetic method using the weight fraction of the standard method.

The hydroxyl group content of the hydroxyl group-containing resin obtained from the components (a) and (b) is 5 to 3
It is preferably 0 mgKOH / g. More preferably, it is 5 to 15 mgKOH / g. If the amount is less than 5 mgKOH / g, the strength of the protective film is reduced, the durability against organic solvents, and the durability against external mechanical stimuli are reduced. In addition, 30mgKOH
If it is not less than / g, the adhesion between the transfer film made of the transfer-printed foil or the design film and the article material is reduced, and the protection of the transfer film is not sufficient.

The hydroxyl group-containing resin obtained from the components (a) and (b) preferably has a molecular weight of 10,000 to 50,000 as a weight average molecular weight in terms of styrene. More preferably, 15,000 to 30,000
It is. The weight average molecular weight in terms of styrene is 10,000
A value of 0 or less is not preferred because the durability of the protective film to mechanical stimuli is reduced. Also, 50,000
In the above case, the finished state such as the leveling property after the formation of the protective film is deteriorated, and the gloss and the appearance are deteriorated.

When an article having a transfer film coated with the protective curable resin composition according to the present invention is used for an automobile exterior part, a radical polymerizable monomer having an ultraviolet absorbing property is added to the resin having a hydroxyl group. It is preferred to copolymerize.

Although it is possible to improve the weather resistance such as the gloss retention of the protective film by adding a commercially available known ultraviolet absorber, the durability of the protective film to mechanical stimulus is reduced. Therefore, it is not preferable to add 2% by weight or more as a solid content in the protective film. The weather resistance of the protective film can be achieved by the addition of an ultraviolet absorber to this extent, but in this case, the protective film is not sufficiently shielded from the ultraviolet light, so that the transfer film is deteriorated by the ultraviolet light. . As a result, the overall weather resistance of the article as a whole is low. Further, when a large amount of the ultraviolet absorber is added, the added ultraviolet absorber migrates onto the surface of the protective film, which is not preferable because whitening and dusting occur. For these reasons, it is preferable that the resin forming the protective film of the present invention contains a copolymer of a radical polymerizable monomer having ultraviolet absorbing properties.

Examples of the radical polymerizable monomer having the ultraviolet absorbing property include ethyl-4-vinyl-α-cyano-β-phenylcyanamate, 3-vinyl salicylic acid, methyl 3-vinyl salicylate,
Vinylacetyl salicylic acid, phenyl 5-acryloxymethyl salicylate, phenyl 5-methacryloxymethyl salicylate, 2-hydroxy-4'-vinylbenzophenone, 2,4-dihydroxy-4-'vinylbenzophenone, 2-hydroxy-4- Acryloxybenzophenone, 2-hydroxy-4-methacryloxybenzophenone, 2-hydroxy-4-acryloxy-ethoxybenzophenone, 2-hydroxy-3-
[3′-methacryloxy-2′-hydroxypropyl]
Benzophenone, 2- (2-hydroxy-5-vinylphenyl) -2H-benzotriazole, 2- (2-hydroxy-3-vinyl-5-methyl) -2H-benzotriazole, 2- (2-hydroxy-5- Isopropenylphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-methylphenyl) -2H-4-vinylbenzotriazole, 2- (2-hydroxy-4-acryloxyphenyl) -2H-benzotriazole, 2-
(2-hydroxy-4-methacryloxyphenyl) -2
H-benzotriazole, 1,3- [2-hydroxy-
4-acryloxyphenyl] di (2H-benzotriazole), 1,3- [2-hydroxy-4-methacryloxyphenyl] di (2H-benzotriazole), 1,3
-[2,6-dihydroxy-4-acryloxyphenyl] di (2H-benzotriazole), 1,3- [2,
6-dihydroxy-4-methacryloxyphenyl] di (2H-benzotriazole), 2- (2-hydroxy-5 [2-hydroxyethylphenyl])-2H-benzotriazole-2-isocyanatoethyl methacrylate) and the like. .

It is preferable that the radical polymerizable monomer having the ultraviolet absorbing property is copolymerized at 0.5 to 20.0% by weight. More preferably, it is 1 to 10% by weight. When the content is 0.5% by weight or less, it is not preferable because the ultraviolet shielding effect is small. When the content is 20.0% by weight or more, a good ultraviolet ray absorbing effect can be obtained, but the radical polymerizable monomer having the above ultraviolet ray absorbing property is expensive, which is not preferable in terms of cost.

Further, the compound having the ultraviolet absorbing ability also decomposes due to radicals generated by the irradiation of ultraviolet rays, so that the ultraviolet absorbing ability decreases over time. Therefore, in the curable resin composition of the present invention, it is particularly important to use a compound having a radical scavenging function in combination.

As the compound having a radical scavenging function, a hindered amine compound having a catalytic scavenging action is preferable. Examples of the hindered amine compounds include bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, poly {2}
-N, N'-di (2,2,6,6-tetramethyl-4-
Piperidinyl) -hexanediamine-4- (1-amino-1,1,3,3-tetramethylbutane) -trialine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3 , 8-Troazaspiro {4,5} decane-2,4-dione.

The compound having a radical scavenging function can be used as an addition to the curable resin composition of the present invention, and when a hindered amine-based light stabilizer having radical polymerizability is used, the compound of the present invention can be used. Can be used by copolymerizing with the resin having a hydroxyl group of the curable resin composition of (1). However, when a compound having a radical scavenging function is used by copolymerization in the curable resin composition of the present invention, it is preferable to use the compound in combination with an addition-type light stabilizer because more excellent weather resistance can be obtained. .

The hindered amine-based light stabilizer used in the curable resin composition of the present invention contains 0.1% in the solid content when a hindered amine-based compound is added or copolymerized.
It is preferable to contain 1 to 5.0% by weight. When the addition of the hindered amine light stabilizer and the copolymerization are used in combination,
The total amount of the hindered amine light stabilizer used for each is preferably 0.1 to 5.0% by weight. More preferably, it is 0.5% by weight to 2.0% by weight. For this reason, it is not preferable to include 0.1% by weight or less of a hindered amine-based light stabilizer in the curable resin composition because the effect of improving weather resistance is small. Also, 5
When used by weight% or more, when the protective coating is applied on the molded product to which the metal layer is transferred, it is preferable because the basic property of the hindered amine compound causes corrosion of the metal foil as the transfer film. Absent.

The resin having a hydroxyl group described above is
It can be obtained by performing radical polymerization in the same manner and under the same conditions as those for radical polymerization of ordinary acrylic resins and vinyl resins. As an example of such a synthesis reaction,
There is a method in which each monomer component is dissolved in an organic solvent and heated with stirring at a temperature of about 60 to 180 ° C. in a nitrogen atmosphere in the presence of a radical polymerization initiator. The reaction time is usually 1
It may be about 10 hours. As the organic solvent, ether solvents, ester solvents, and hydrocarbon solvents can be used. As the radical polymerization initiator, those usually used can be used, and examples thereof include peroxides such as benzoyl peroxide and t-butylperoxy-2-ethylhexanoate, and azobisisobutyronitrile. And azo compounds such as azobisdimethylvaleronitrile.

The resin having a hydroxyl group is mixed with an isocyanate prepolymer and coated as a curable resin composition to form a protective film. Examples of the isocyanate-based compound include hexamethylene diisocyanate, isophorone diisocyanate, and the like. Burette type adducts such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-methylenebis (cyclopexyl isocyanate), xylylene diisocyanate, isocyanuric ring type, and polyhydric alcohol adducts. Of these, burette-type adducts, isocyanuric ring types, and polyhydric alcohol additions of non-yellowing diisocyanate compounds such as hexamethylene diisocyanate, isophorone diisocyanate, and 4,4'-methylenebis (cyclopexyl isocyanate) are preferable. Things. It is also possible to use blocked isocyanates.

The ratio of mixing the isocyanate prepolymer with the hydroxyl group-containing resin is preferably an isocyanate compound equivalent to 0.5 to 2.0 equivalents to 1 equivalent of the hydroxyl group of the hydroxyl group resin. 0.5
If the amount is less than the equivalent, the crosslinking reaction becomes insufficient and the durability such as mechanical durability, chemical resistance, and weather resistance decreases, which is not preferable. On the other hand, if it is 2.0 equivalents or more, it is not preferable because the protective film is softened in the initial stage of drying.

The curable resin composition for protecting a transfer film of the present invention may contain, if necessary, a known coating surface modifier, fluidity modifier, curing catalyst, extender, coloring pigment, metal pigment, mica powder. Pigments, dyes, organic solvents and the like can be added. Further, the curable composition includes, for example, hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, dioxane, ethylene glycol diethyl ether and the like. The ether-based solvent or the like may be diluted with a single or mixed solvent, and then applied by a coating method such as spray coating, roll coating, and brush coating.

The article coated with the curable resin composition is subjected to normal temperature or forced drying to complete the formation of the protective film. Here, the forced drying means a step of drying using a drying furnace or the like heated to a normal temperature or higher, and is a usual drying method. Although the upper limit of the drying temperature during drying depends on the coating material, it is generally the same as the upper limit temperature of plastic coating.

[0041]

EXAMPLES Hereinafter, some examples of the present invention will be described, but the present invention is not limited to these examples. Example 1 [Synthesis of hydroxyl-containing resin used for protection of transfer-printed molded article]-1-liter round bottom 4 equipped with a nitrogen inlet tube, a thermometer, a cooling tube, a dropping funnel, and a stirring device
In a one-necked flask, 400.0 g of toluene was charged, and 10
Heated to 0 ° C. Methyl methacrylate 2 prepared separately
36.0 g, n-butyl methacrylate 80.0 g, methacrylic acid 4.0 g, FM-4 (Epsilon caprolactone modified radical polymerizable monomer manufactured by Daicel Chemical Co., Ltd. (average modification number: 4)) 80.0 g, ABN-E (Nippon Hydrazine Industry) A mixture consisting of 12.0 g of an azo compound (manufactured by Corporation) was added to the flask over 4 hours using a dropping funnel. After completion of the addition, ABN-E was added 1.0 g each for 20 minutes every 100 minutes for a total of 5 times, and the reaction was terminated by maintaining the temperature in the flask at 100 ° C. for 120 minutes, and the resin solution having a hydroxyl group of Example 1 was added. I got

In the resin having a hydroxyl group in Example 1, the estimated value of the glass transition temperature of a polymer obtained by polymerizing components other than the monomer modified with caprolactone was 84 ° C.
And the hydroxyl value is 20 mgKOH / g. Further, the weight average molecular weight in terms of polystyrene is 22,000, and a monomer having an ultraviolet absorbing property is not copolymerized.

[Preparation of Curable Resin Composition for Protecting Transfer-Printed Molded Article]-Resin Solution 7 Having Hydroxyl Group
5.0% by weight, methyl ethyl ketone 10.0% by weight, toluene 14.99% by weight, dibutyltin dilaurate 0.
The clear resin composition of Example 1 was obtained by mixing 01% by weight. Separately, 30% by weight of TPA-100 (isocyanuric ring type isocyanate compound of hexamethylene diisocyanate manufactured by Asahi Kasei Corporation), 30.0% by weight of 24A-100 (buret addition type isocyanate compound of hexamethylene diisocyanate manufactured by Asahi Kasei Corporation)
The curing agent of Example 1 was obtained by mixing 20.0% by weight of toluene and 20.0% by weight of ethyl acetate. Separately ethyl acetate 2
A thinner for dilution of Example 1 was obtained by mixing 0.0% by weight, 30.0% by weight of methyl isobutyl ketone, 30.0% by weight of toluene, and 20.0% by weight of Solvesso 150 (hydrocarbon-based mixed solvent). .

The curing agent is blended in a ratio of 1.2 equivalents to 1.0 equivalents of the hydroxyl groups contained in the resin having a hydroxyl group.
4, the mixture was diluted with the thinner until 11.5 seconds to obtain a curable resin composition for protecting a transfer-printed plastic molded article of Example 1.

Example 2: [Synthesis of a resin having a hydroxyl group used for protection of a transfer-printed molded article]-400.0 g of toluene was charged using the same polymerization apparatus as in Example 1,
Heated to 100 ° C. 96.0 g of separately prepared methyl methacrylate, 120.0 g of n-butyl methacrylate
g, 4.0 g of methacrylic acid, n-butyl acrylate 1
A mixture comprising 00.0 g, 80.0 g of FM-4 (epsilon caprolactone-modified radical polymerizable monomer manufactured by Daicel Chemical Co., Ltd. (average modification number: 4)), and 12.0 g of ABN-E (azo compound manufactured by Nippon Hydrazine Industry Co., Ltd.) It was added to the flask over 4 hours using a dropping funnel. After the addition, AB every 20 minutes for 100 minutes
NE was added 5 times in total of 1.0 g each time, and the reaction was terminated while keeping the temperature in the flask at 100 ° C. for 120 minutes to obtain a resin solution having a hydroxyl group of Example 2.

The estimated value of the glass transition temperature of the polymer obtained by polymerizing the components other than the monomer modified with caprolactone in the resin having a hydroxyl group in Example 2 is 24 ° C., and the hydroxyl value is 20 mgKOH / g. The weight average molecular weight in terms of polystyrene is 20,000.
At 0, the UV absorbing monomer is not copolymerized.

[Preparation of Curable Resin Composition for Protecting Transfer-Printed Molded Article] A clear resin composition of Example 2 was obtained in the same manner as in Example 1. Further, a curable resin composition for protecting a transfer-printed molded article of Example 2 was obtained in the same manner as in Example 1 using the curing agent of Example 1 and a thinner for dilution.

Example 3: [Synthesis of a resin having a hydroxyl group used for protection of a transfer-printed molded article]-400.0 g of toluene was charged using the same polymerization apparatus as in Example 1,
Heated to 100 ° C. 236.0 g of separately prepared methyl methacrylate, 60.0 g of n-butyl methacrylate
g, 2-hydroxyethyl methacrylate 20.0 g,
It consists of 4.0 g of methacrylic acid, 80.0 g of FM-4 (Epsilon caprolactone modified radical polymerizable monomer manufactured by Daicel Chemical Industries, Ltd. (average modification number: 4)), and 12.0 g of ABN-E (azo compound manufactured by Nippon Hydrazine Industry Co., Ltd.). The mixture was added to the flask using a dropping funnel over 4 hours. After the addition is completed, every 20 minutes, 100 minutes of ABN-E
Was added 5 times in total, and the temperature in the flask was kept at 100 ° C. for 120 minutes to complete the reaction.
A resin solution having a hydroxyl group was obtained.

In the resin having a hydroxyl group in Example 3, the estimated value of the glass transition temperature of a polymer obtained by polymerizing components other than the monomer modified with caprolactone is 86 ° C., and the hydroxyl value is 40 mgKOH / g. The weight average molecular weight in terms of polystyrene is 22,000.
At 0, the UV absorbing monomer is not copolymerized.

[Preparation of Curable Resin Composition for Protection of Transfer-Printed Molded Article] A clear resin composition of Example 3 was obtained in the same manner as in Example 1. Further, a curable resin composition for protecting a transfer-printed molded article of Example 3 was obtained in the same manner as in Example 1 using the curing agent of Example 1 and a thinner for dilution.

Example 4: [Synthesis of Hydroxyl-Resin-Based Resin Used for Protecting Transfer-Printed Molded Article] 400.0 g of toluene was charged using the same polymerization apparatus as in Example 1,
Heated to 110 ° C. 236.0 g of separately prepared methyl methacrylate, 80.0 g of n-butyl methacrylate
g, 4.0 g of methacrylic acid, 80.0 g of FM-4 (Epsilon caprolactone modified radical polymerizable monomer manufactured by Daicel Chemical Co., Ltd. (average modification number: 4)), 40.0 g of ABN-E (azo compound manufactured by Nippon Hydrazine Industry Co., Ltd.) Was added to the flask using a dropping funnel over 4 hours. After the addition was completed, 5.0 g of ABN-E was added every 20 minutes for 100 minutes for a total of 5 times.
The reaction was terminated by maintaining the temperature in the flask at 110 ° C. for 20 minutes, and the hydroxyl group-containing resin solution of Example 4 was obtained.

The estimated value of the glass transition temperature of the polymer obtained by polymerizing components other than the monomer modified with caprolactone in the resin having a hydroxyl group of Example 4 is 86 ° C., and the hydroxyl value is 20 mgKOH / g. The weight average molecular weight in terms of polystyrene is 5,500.
In this case, the monomer having ultraviolet absorbing properties is not copolymerized.

[Preparation of Curable Resin Composition for Protection of Transfer-Printed Molded Article] A clear resin composition of Example 4 was obtained in the same manner as in Example 1. Further, a curable resin composition for protecting a transfer-printed molded article of Example 4 was obtained in the same manner as in Example 1 using the curing agent of Example 1 and a thinner for dilution.

Example 5: [Synthesis of a resin having a hydroxyl group used for protecting a transfer-printed molded article]-560.0 g of toluene was charged using the same polymerization apparatus as in Example 1,
Heated to 90 ° C. 177.0 g of separately prepared methyl methacrylate, 60.0 g of n-butyl methacrylate,
It consists of 3.0 g of methacrylic acid, 60.0 g of FM-4 (epsilon caprolactone modified radical polymerizable monomer manufactured by Daicel Chemical Industries, Ltd. (average modification number: 4)), and 3.0 g of ABN-E (azo compound manufactured by Nippon Hydrazine Industry Co., Ltd.). The mixture was added to the flask using a dropping funnel over 90 minutes. ABN- every 180 minutes after completion of addition
E was added 1.0 g each three times in total, and the temperature in the flask was kept at 90 ° C. for further 240 minutes to terminate the reaction.
A resin solution having a hydroxyl group was obtained.

In the resin having a hydroxyl group in Example 5, the estimated value of the glass transition temperature of a polymer obtained by polymerizing components other than the monomer modified with caprolactone is 86 ° C., and the hydroxyl value is 20 mgKOH / g. The weight average molecular weight in terms of polystyrene is 78,00.
At 0, the UV absorbing monomer is not copolymerized.

[Preparation of Curable Resin Composition for Protection of Transfer-Printed Molded Article] A clear resin composition of Example 5 was obtained in the same manner as in Example 1. Further, a curable resin composition for protecting a transfer-printed molded product of Example 5 was obtained in the same manner as in Example 1 using the curing agent of Example 1 and a thinner for dilution.

Example 6: [Synthesis of a resin having a hydroxyl group used for protection of a transfer-printed molded article]-400.0 g of toluene was charged using the same polymerization apparatus as in Example 1,
Heated to 100 ° C. 216.0 g of separately prepared methyl methacrylate, 92.0 g of n-butyl methacrylate
g, methacrylic acid 4.0 g, FM-4 (Daicel Chemical Co., Ltd.)
80.0 g of epsilon caprolactone-modified radical polymerizable monomer (average modification number: 4) manufactured by Epsilon Caprolactone Co., Ltd .; A mixture consisting of 20.0 g of a benzotriazole-based radical polymerizable monomer having the same and 12.0 g of ABN-E (an azo compound manufactured by Nippon Hydrazine Industry Co., Ltd.) was added to the flask over 4 hours using a dropping funnel. After completion of the addition, 1.0 g of ABN-E was added 5 times in total for 20 minutes every 100 minutes, and the reaction was terminated by maintaining the temperature in the flask at 100 ° C. for further 120 minutes.
A resin solution having a hydroxyl group of Example 6 was obtained.

In the resin having a hydroxyl group in Example 6, the estimated value of the glass transition temperature of a polymer obtained by polymerizing components other than the monomer modified with caprolactone is 86 ° C., and the hydroxyl value is 20 mgKOH / g. The weight average molecular weight in terms of polystyrene is 22,000.
0 means that 5% by weight of an ultraviolet absorbing monomer is copolymerized.

[Preparation of Curable Resin Composition for Protection of Transfer-Printed Molded Article] A clear resin composition of Example 6 was obtained in the same manner as in Example 1. Further, a curable resin composition for protecting a transfer-printed molded article of Example 6 was obtained in the same manner as in Example 1 using the curing agent of Example 1 and a thinner for dilution.

Example 7: [Synthesis of Hydroxyl Resin Used for Protecting Transfer-Printed Molded Product]-400.0 g of toluene was charged using the same polymerization apparatus as in Example 1,
Heated to 100 ° C. 216.0 g of separately prepared methyl methacrylate, 92.0 g of n-butyl methacrylate
g, methacrylic acid 4.0 g, FM-4 (Daicel Chemical Co., Ltd.)
80.0 g of epsilon caprolactone modified radical polymerizable monomer (average number of modification: 4) manufactured by Epsilon Caprolactone Co., Ltd .; 2- (2-hydroxy-5 {2-hydroxyethylphenyl})-2H-benzotriazole-2-ethyl methacrylate A mixture consisting of 20.0 g of a benzotriazole-based radical polymerizable monomer having the same and 12.0 g of ABN-E (an azo compound manufactured by Nippon Hydrazine Industry Co., Ltd.) was added to the flask over 4 hours using a dropping funnel. After the addition was completed, ABN-E was added 1.0 g every 20 minutes for a total of 5 times for a total of 5 times, and the reaction was terminated by keeping the temperature in the flask at 100 ° C. for 120 minutes. I got

The estimated value of the glass transition temperature of the polymer obtained by polymerizing components other than the monomer modified with caprolactone in the resin having a hydroxyl group of Example 7 is 86 ° C., and the hydroxyl value is 20 mgKOH / g. The weight average molecular weight in terms of polystyrene is 22,000.
0 means that 5% by weight of an ultraviolet absorbing monomer is copolymerized.

[Preparation of Curable Resin Composition for Protecting Transfer-Printed Molded Article]-Resin Solution Having Hydroxyl Group 7
5.0% by weight, SANOL LS-292 (a hindered amine light stabilizer bis (1,2,2,6,6) manufactured by Sankyo Co., Ltd.)
-Tetramethyl-4-piperidinyl) sebacate) 1.
2 wt%, methyl ethyl ketone 10.0 wt%, toluene 13.79 wt%, dibutyltin dilaurate 0.01
By weight, the clear resin composition of Example 7 was obtained.

The protective curable resin composition of the transfer-printed molded article of Example 7 was obtained in the same manner as in Example 1 using the curing agent of Example 1 and the thinner for dilution. Example 7 is an example in which the curable resin composition contains 1% by weight as a solid content of a hindered amine light stabilizer.

[Comparative example]

Comparative Example 1 [Synthesis of Hydroxyl Resin Used for Protection of Transfer-Printed Molded Product] —400.0 g of toluene was charged using the same polymerization apparatus as in Example 1,
Heated to 100 ° C. 296.0 g of separately prepared methyl methacrylate, 80.0 g of n-butyl methacrylate
g, 4.0 g of methacrylic acid, 20.0 g of 2-hydroxyethyl methacrylate, and 12.0 g of ABN-E (azo compound manufactured by Nippon Hydrazine Industry Co., Ltd.) were added to the flask over 4 hours using a dropping funnel. did. After the addition was completed, ABN-E was added 1.0 g every 20 minutes every 100 minutes for a total of 5 times, and the reaction was terminated by keeping the temperature in the flask at 100 ° C. for 120 minutes, and the hydroxyl-containing resin solution of Comparative Example 1 was added. I got

The estimated value of the glass transition temperature of the resin having a hydroxyl group of Comparative Example 1 was 86 ° C., and the hydroxyl value was 20 mg KO.
H / g. Further, the weight average molecular weight in terms of polystyrene is 20,000, and a monomer having an ultraviolet absorbing property is not copolymerized.

[Preparation of Curable Resin Composition for Protecting Transfer-Printed Molded Article] A clear resin composition of Comparative Example 1 was obtained in the same manner as in Example 1. Further, a curable resin composition for protecting a transfer-printed molded product of Comparative Example 1 was obtained in the same manner as in Example 1 using the curing agent of Example 1 and a thinner for dilution.

Comparative Example 2: [Synthesis of Hydroxyl Resin Used for Protection of Transfer-Printed Molded Article] Toluene (400.0 g) was charged using the same polymerization apparatus as in Example 1,
Heated to 100 ° C. 256.0 g of separately prepared methyl methacrylate, 40.0 g of n-butyl methacrylate
g, 4.0 g of methacrylic acid, 20.0 g of 2-hydroxyethyl methacrylate, 80.0 g of FM-40 (epsilon caprolactone-modified radical polymerizable monomer manufactured by Daicel Chemical Co., Ltd. (average modification number: 40)), and ABN-E (Nippon Hydrazine Industry) A mixture consisting of 12.0 g of an azo compound (manufactured by Co., Ltd.) was added to the flask over 4 hours using a dropping funnel. After the addition is complete, AB every 20 minutes for 100 minutes
NE was added 5 times in total of 1.0 g each time, and the reaction was terminated by keeping the temperature in the flask at 100 ° C. for 120 minutes to obtain a hydroxyl group-containing resin solution of Comparative Example 2.

The estimated value of the glass transition temperature of the polymer obtained by polymerizing a component other than the monomer modified with prolactone in the hydroxyl group-containing resin of Comparative Example 2 was 92 ° C., and the hydroxyl value was 20 mg KOH / g. is there. The weight average molecular weight in terms of polystyrene is 24,000.
At 0, the UV absorbing monomer is not copolymerized.

[Preparation of Curable Resin Composition for Protection of Transfer-Printed Molded Article] A clear resin composition of Comparative Example 2 was obtained in the same manner as in Example 1. Further, a curable resin composition for protection of a transfer-printed molded product of Comparative Example 2 was obtained in the same manner as in Example 1 using the curing agent of Example 1 and a thinner for dilution.

[Coating Film Evaluation Method] (A) Paint Preparation and Coating Drying—The curable coating compositions obtained in the above Examples and Comparative Examples were dried by air spray coating on the molded product on which the metal foil was transferred and printed. The coating was uniformly applied so that the thickness of the cured film later became 20 μm. After the air spray was completed, the mixture was allowed to stand for 5 minutes and then dried in a box-type drying oven at 80 ° C. for 30 minutes. Furthermore, the drying process was completed by leaving it to stand at room temperature for 4 days, and various tests were performed. Table 1 shows the test results.

(B) Coating film test items and evaluation method Adhesion test: 1 mm × 1 mm × 100 cross cuts, evaluated from the number of crosses remaining after the cellophane tape peeling test. Impact resistance test: The test environment was maintained at 20 ° C, and a 300 g spherical iron ball was dropped vertically on a protectively coated product. did. Flexibility test: relatively evaluated from the state of cracks and cracks in the coating film caused by bending the molded article on which the protective coating film was applied. Solvent resistance test: Judgment was made from the surface state after immersion in Nisseki regular gasoline at 20 ° C. for 30 minutes and the state of adhesion by cross cut. Weather resistance: Accelerated weathering test was conducted with a sunshine weatherometer under the cycle conditions of black panel temperature of 83 ° C, continuous irradiation, and rainfall of 5 minutes every 55 minutes, and the weathering deterioration of the transfer foil and the protective film was relatively evaluated. . Finish appearance: The smoothness of the finished state was relatively evaluated visually. Storage stability: 5 ° C with the paint before mixing the curing agent in a closed state
And the change of the paint over time was relatively evaluated.

(C) Evaluation criteria for test evaluation: extremely good ：: good Δ: slightly poor but usable range ×: defective

[0073]

As described above, according to the present invention, a transfer film of a transfer pattern transferred to an article surface is cured by a curable resin comprising a hydroxyl group-containing resin composed of a specific component and an isocyanate prepolymer. By coating with the composition, the problems with conventional protective coating with acrylic urethane resin, such as durability against solvents, adhesion of the transfer film to the molded product, mechanical strength of the protective coating, and practical use It has become possible to provide a method for protecting a transfer-printed transfer film that imparts sufficient weather resistance. This has made it possible to apply the article provided with the transfer film to automobile exterior parts.

Table 1

Claims (8)

[Claims] In a resin composition forming a coating film for protecting a transfer film formed on an article, a hydroxyl group modified by a caprolactone monomer having an average mole number of 1 mol or more and 20 mol or less is used. A polymer obtained by copolymerizing a radical polymerizable monomer (a) contained therein with a radical polymerizable monomer (b) having a hydroxyl group modified by the caprolactone-based monomer and a polymerizable radical polymerizable monomer (b); A curable resin composition for protecting a transfer film, comprising a polymer. 2. A curable resin for protecting a transfer film, wherein the polymer obtained by polymerizing the radical polymerizable monomer (b) according to claim 1 has a glass transition temperature of 50 ° C. or higher. Composition. 3. The curable resin composition according to claim 1, which has a hydroxyl value of 5 to 30 mg KOH.
/ G hydroxyl group, the curable resin composition for protecting a transfer film. 4. The curable resin composition according to claim 1, wherein the curable resin composition is 1 in styrene equivalent.
A curable resin composition for protecting a transfer film, which has a weight average molecular weight of 0000 to 50,000. 5. The curable resin composition according to claim 1, wherein the radical polymerizable monomer having ultraviolet absorbability is copolymerized in an amount of 0.5 to 20.0% by weight. A curable resin composition for protecting a transfer film. 6. The curable resin composition according to any one of claims 1 to 5, wherein the curable resin composition has a solid content of 0.1 to 10%.
A curable resin composition for protecting a transfer film, comprising 5.0% by weight of a hindered amine light stabilizer. 7. An article, wherein at least the transfer film is covered with the protective curable resin composition according to any one of claims 1 to 6. 8. A method of protecting a transfer film, wherein at least the transfer film is covered and protected by using the curable resin composition for protection according to claim 1. .