KR20130049154A - Active energy ray-curable resin, active energy ray-curable resin composition, active energy ray-curable hard coating agent, cured film using them, decoration film laminated with the cured film and plastic injection-molded product using the decoration film - Google Patents

Abstract

PURPOSE: An active energy ray-curable resin is provided to improve processability in injection molding, thereby providing an injection-molded plastic product with excellent hard-coated surface, high elongation, and high hardness. CONSTITUTION: An active energy ray-curable resin is obtained by conducting a reaction of alpha, beta-unsaturated carboxylic acid to a copolymer with a branched structure and has an average molecular weight of 10,000-100,000. The copolymer is obtained by a reaction of an epoxy group-containing (meth)acrylate-based monomer and a macro-monomer which has an unsaturated double bond at one terminal, does not contains an epoxy group and carboxyl group, and has a weight average molecular weight of 1,000-20,000, with a mixing ratio of 80:20-40:60. The energy ray-curable resin composition contains the active energy ray-curable resin and a photopolymerization initiator.

Description

Active energy ray-curable resin, active energy ray-curable resin composition, active energy ray-curable hard coat agent, cured film using them, decorative film laminated with cured film, and plastic injection molded product using decorative film {ACTIVE ENERGY RAY-CURABLE RESIN, ACTIVE ENERGY RAY-CURABLE RESIN COMPOSITION, ACTIVE ENERGY RAY-CURABLE HARD COATING AGENT, CURED FILM USING THEM, DECORATION FILM LAMINATED WITH THE CURED FILM AND PLASTIC INJECTION-MOLDED PRODUCT USING THE DECORATION FILM}

The present invention relates to an active energy ray-curable resin having a processability, an active energy ray-curable hard coating agent, a cured film using them, a decorative film on which a cured film is laminated, and a plastic injection molded article using the decorative film. will be. More specifically, not a two-dimensional decorating method such as painting or printing, but a method of simultaneously decorating with the injection molding of a resin such as plastic in a mold (in mold: In Mold), that is, in-mold decorating, Activation energy used in decorative film used in in-mold transfer, in-mold labeling, in-mold molding, film insert molding, etc. It is a pre-curable hard coat agent, and the article shape | molded using it.

In recent years, in plastic injection molded articles, such as a mobile phone terminal, a PC case, and an in-car trim, both a complicated design and the difficulty of flaw of a plastic molded article are calculated | required. For this reason, the in-mold decorating method which is more complicated than the two-dimensional decorating methods, such as spray coating and printing, and which can improve designability by various texture is attracting attention. The in-mold decorating method inserts a decorative film for decorating the surface of a molded article in the mold at the time of injection molding, injects and integrates molten plastic resin, and decorates the surface of the plastic molded article. Therefore, it can classify into following (1) and (2). One method is to use a decorative film in which a hard coat layer or a pattern layer is laminated on a release substrate, and then insert it into a mold, peel off the release substrate after injection molding, and leave a hard coat layer and a pattern layer on the surface of the plastic molded article. It is called mold decorating). Another is (2) a method (called IMF) that inserts a decorative film having a pattern layer or a hard coat layer in a PET (polyethylene terephthalate) film, is injected into a mold, and affixed to a plastic molded article.

When both of said (1) and (2) are injection-molded in a metal mold | die, the in-mold decorated film is extended | stretched to the shape along the metal mold inner surface. In general, the higher the hard coat property, the harder and brittle properties become, and cracks tend to occur due to stress at the time of stretching. Specifically, cracks are likely to occur at deep drawing or sharp corner portions of three-dimensional curved surfaces, and hard coatability is degraded or designability is limited with respect to the processability of the decorative film.

In recent years, in order to differentiate products, in order to complicate design and to find more flaws, both of processability and hard coatability are indispensable, and various methods have been proposed. For example, the method of adjusting the crosslinking density by the compounding composition of a trifunctional or more (meth) acryl oligomer and a 1-2 functional (meth) acryl monomer is proposed (refer patent document 1). According to this method, although the hard coat film which has the high surface hardness and the workability which can follow the deformation | transformation at the time of shaping | molding is proposed, the surface hardness and workability are trade-off relationship, There was a problem that it was compelled to compromise with balance.

Moreover, the polymer (meth) acrylate whose molecular weight 5,000-50,000 (meth) acryloyl equivalent is 200 g / eq or more and 800 g / eq or less, and the molecular weight 1,000-10,000 (meth) acryloyl equivalent 100 g / eq or more 200 g / eq The method of mix | blending less than polyfunctional urethane (meth) acrylate is proposed (refer patent document 2). According to this method, in the method of said (1), it is excellent in abrasion resistance and chemical-resistance, and does not produce a crack in the curved part of a molded article. However, the process of said (2) did not satisfy workability.

Moreover, the method of providing workability by mix | blending non-reactive resin which does not have a radically polymerizable double bond with a (meth) acrylate monomer is also proposed (refer patent document 3). However, when mix | blending such a non-reactive resin and a plastic resin, although workability improves, it was lacking in the high hard coat property until a recent demand.

Thus, although various approaches have been made in any of the above methods (1) and (2), they are all hardening methods only to soften the hard coat layer, and the hard coat property of the flaw hardness originally required for the hard coat layer. Another problem of this deterioration occurred. Active energy resins having both processability and hard coatability have not been proposed.

On the other hand, when coating an active energy ray-curable resin on a thermoplastic film, the active energy ray-curable resin which adjusted the viscosity with the organic solvent is apply | coated, the organic solvent is volatilized by heating, it is made into a dry film, and it winds up in roll shape once, We may save. In that case, when the conveyance roller of the applicator for film conveyance touches a dry film, when the adhesive force of a dry film is high, it may stick to a roller and a trouble may arise in a manufacturing process. Moreover, while the roll rolled up is preserve | saved, a dry film sticks to the film back surface side, and it may become difficult to peel off from a roll (it is called blocking). The adhesive force of such a dry film is called tackiness, and when the adhesiveness is high, the above-mentioned trouble is easy to occur. On the contrary, when the adhesive film is low, it is difficult to occur and the handling is good, contributing to the improvement of manufacturing efficiency and the yield.

In order to prevent such troubles, a proposal has been made in which active fine particles of inorganic energy such as silica are mixed with an active energy ray-curable resin to form irregularities on the surface of the coating film to reduce the contact area between the layers, thereby reducing adhesiveness and preventing blocking. (Patent Document 4).

Although the method of suppressing the contact area is very effective, when the unevenness of the particles appears on the surface, the coating film thickness must be set below the particle diameter, and the coating film must be made thin, so that sufficient hard coat property cannot be provided, and the inorganic fine particles In order to mix | blend, a cured film becomes a brittle physical property and is not suitable for the film for shaping | molding which processability is required.

In order to improve the said subject, the method of forming an unevenness | corrugation on the surface of a coating film using the phase separation at the time of mixing two types of active energy ray resins from which solubility differs is proposed (patent document 5). Although it does not depend on coating film thickness, adhesiveness is low and it becomes difficult to block, but since phase separation, transparency of a cured film tends to be impaired and optical characteristics tend to worsen.

Moreover, there exists a proposal of the organic-inorganic composite resin composition of the copolymer which has a photopolymerizable functional group in a side chain, and a silica inorganic fine particle (patent document 6). The copolymer has excellent adhesiveness with a weight average molecular weight of 5000 to 100000 and is cured after processing without the need to irradiate and harden active energy ray prior to forming, so that it has good processability and hard coatability, but it is about adhesiveness and processability. There was still room for improvement.

Moreover, polyfunctional isocyanate is mix | blended with the active energy ray curable resin of (meth) acryloyl equivalent 100-300 g / eq, the hydroxyl value 20-500, and the weight average molecular weight 500-50,000, and a heating of an active energy ray curable resin There exists a technique that a hydroxyl group and polyfunctional isocyanate can be thermally crosslinked, and the adhesiveness of a dry film can be suppressed and blocking can be suppressed (patent document 7). However, since the reaction of hydroxyl group and isocyanate proceeds at room temperature, storage stability is poor. Moreover, a polyfunctional isocyanate component may become a factor which reduces hard coat property and adhesiveness.

As described above, active energy ray-curable resins which form a cured film having low adhesiveness without compromising the workability and the hard coatability which are related to the trade-off relationship that have been difficult in the past and without impairing the optical properties have not yet been developed.

Japanese Patent Publication No. 2011-148964 Japanese Patent Publication No. 2004-123780 Japanese Patent Publication No. 2008-208154 Japanese Patent Publication No. 2004-42653 Japanese Patent Publication No. 2007-182519 Japanese Patent Laid-Open No. 2001-206925 Japanese Patent Laid-Open No. 1998-58895

The present invention is an active energy ray-curable resin suitable for use in a decorative film capable of providing the flawlessness of a molded article with the complex design required for a plastic injection molded article in recent years, and is compatible with processability and hard coatability which have been difficult in the past. A low adhesion cured film is formed without impairing optical properties.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the above-mentioned subject, the inventors made unsaturated double bond in the one end which consisted of the epoxy group containing (meth) acrylate type monomer (A) and the polymerizable monomer which does not contain an epoxy group as a main component. It has a branched structure having a specific weight average molecular weight obtained by adding α, β-unsaturated carboxylic acid (C) to the epoxy group of the A / B copolymer obtained by radical copolymerization of the macromonomer (B) at a specific weight ratio. It was found that the problem was solved by the active energy ray-curable resin.

That is, this invention 1 has the epoxy group containing (meth) acrylate type monomer (A) and the macromonomer (B) of the weight average molecular weight 1,000-20,000 which has an unsaturated double bond in either terminal and does not contain an epoxy group and a carboxyl group. It is obtained by making (alpha), (beta)-unsaturated carboxylic acid (C) react with the copolymer which has a branched structure obtained by making a weight ratio (A) :( B) react at 80: 20-40: 60, and a weight average molecular weight is 10,000- It is an active energy ray hardening type resin which is 100,000.

This invention 2 is active energy ray hardening type resin which is a radical copolymer which has a macromonomer (B) in this invention 1 which has a radically polymerizable group which has the terminal structure represented by General formula (1).

　

　

(Wherein X is a compound moiety having a radical polymerizable group, R ₁ is H or CH ₃ , R ₂ is —C (═O) OR ₃ or a phenyl group, R ₃ is —CH ₃ , —CH ₂ CH (CH ₃ ) Any structure selected from the group of ₂ , -C (CH ₃ ) ₃ , and-(CH ₂ ) _m CH ₃ (m represents an integer of 1 to 17. n represents an integer)

The present invention 3 is an active energy ray-curable resin composition containing the active energy ray-curable resin and the photopolymerization initiator according to the present invention 1 or 2.

This invention 4 is active energy ray hardening type resin composition which further contains a polyfunctional (meth) acrylate in this invention 3.

This invention 5 is an active energy ray hardening-type hard-coat agent containing the active energy ray hardening type resin composition of this invention 3 or 4.

This invention 6 is a cured film obtained by making it harden | cure by irradiating an active energy ray to the active energy ray hardening-type hard coat agent of this invention 5.

This invention 7 is an in-mold decorated film in which the cured film of this invention 6 was laminated | stacked.

This invention 8 is a plastic injection molded article using the in-mold decorated film of this invention 7.

By using the active energy ray resin which this invention provides, and the hard-coat agent using the same, hardening shrinkage is small even after active energy ray hardening, film elongation is high, and is equivalent to the conventional active energy ray hardening type hard coat agent. Good hard coat having hard coatability, good workability in which cracking is unlikely to occur with respect to stress during bending and drawing in the injection molding process, and a pencil hardness equivalent to that of conventional general-purpose hard coat agents It is possible to provide a decorative film having both sex, and it is possible to provide a surface that is difficult to be damaged without restricting the design of a molded product such as a complicated shape or a deep drawing process which has been difficult until now. Moreover, a dry film with very low adhesiveness can be obtained without impairing optical properties, and since sticking with a conveying roller such as an applicator and blocking after roll winding can be suppressed, good workability can be provided with high efficiency. .

The active energy ray-curable resin of the present invention is a macro having no epoxy group having an unsaturated double bond at either end (also referred to as one end) of an epoxy group-containing (meth) acrylate-based monomer (hereinafter referred to as component (A)). Α, β-unsaturated carboxylic acid (hereinafter (C) component) to a polymer having a branched structure obtained by reacting a monomer (hereinafter referred to as component (B)) in a weight ratio (A) :( B) at 80:20 to 40:60 It is obtained by reacting), and a weight average molecular weight is 10,000-100,000.

The said (A) component is a compound which has at least 1 epoxy group and 1 unsaturated double bond in a molecule | numerator. Specifically, glycidyl (meth) acrylate, (beta) -methylglycidyl (meth) acrylate, 3, 4- epoxycyclohexyl methyl (meth) acrylate, 1-vinyl-3, 4-epoxycyclohexane, etc. Can be mentioned. Among these, glycidyl (meth) acrylate is preferable in view of availability and procurement cost.

As said (B) component, if it has a macromonomer with a weight average molecular weight 1,000-20,000 which has an unsaturated double bond in either terminal and does not contain an epoxy group and a carboxyl group, a well-known thing can be used. When it contains an epoxy group, in addition reaction with (C) component, it has an unsaturated double bond group bridge | crosslinked by active energy ray irradiation also in a side chain like a main chain, and hard coat property improves, but workability will fall. Moreover, if it is a chemical structure containing a carboxyl group, in the addition reaction process of (alpha), (beta)-unsaturated carboxylic acid, addition reaction of the epoxy group of a main chain and a carboxyl group of a side chain will arise and gelatinize. Moreover, the pencil hardness which shows the hard coat property of a cured film will fall that the weight average molecular weight is less than 1,000, and when the weight average molecular weight exceeds 20,000, compatibility with (A) component and an organic solvent will worsen.

Specific examples of the component (B) include macromonomers composed of radical copolymers of monomers having unsaturated double bonds such as TOA synthetic macromonomer AA-6, AB-6, AY-707S, and nitrogen Macromonomer consisting of condensates of dimethylsiloxane contained in ilaplane FM-0711 and FM-0721, macromonomer composed of ring-opened polymer of ε-caprolactone contained in Daicel Chemical Industries, Inc. The macromonomer etc. which consist of addition polymer of alcohol and alkylene oxide etc. which are contained in oil Brenma PME-4000, PSE-1300, etc. are mentioned.

The manufacturing method of the said (B) component is not specifically limited, For example, it can synthesize | combine by the method proposed by Unexamined-Japanese-Patent No. 1996-73577 and Unexamined-Japanese-Patent No. 2001-64318. Specifically, in the presence of thioalcohol serving as a chain transfer agent, a copolymerization reaction of a monomer having an unsaturated double bond is carried out, and after synthesis of a copolymer polymer having a hydroxyl group introduced at least at one end, 2-methacryloyloxyethyl isocyanate and Methacrylic acid chloride etc. can be added and reacted with a hydroxyl group, and the polymer which one end has a radical copolymerizable group can be obtained. Moreover, the macromonomer manufacturing method which does not use a chain transfer agent etc. by radical polymerization at high temperature is proposed by Toa Synthetics Co., Ltd., Kawai et al. (Toa synthesis research yearbook # TREND2002 # 5-p.2-10). It can manufacture by either of these methods.

It does not specifically limit as a monomer which has an unsaturated double bond used as a raw material of the said (B) component, Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) ) Acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) Acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerin mono (Meth) acrylate, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, cyclohexyl (meth) acrylate, 4-tert- butylcyclohexyl (meth) acrylic Latex, N-acryloyloxyethylhexahydrophthalimide, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, polysiloxane mono (Meth) acrylate etc., and styrene are mentioned, It is also possible to use 1 type or 2 or more types together. Among them, from the viewpoint of both raw material cost and workability and hard coatability, methyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate and styrene are preferable.

It is preferable that the said (B) component is a radical copolymer which has radical polymerizability which has a terminal structure represented by General formula (1).

　

　

(Wherein X is a site having a radical polymerizable group, R ₁ is H or CH ₃ , R ₂ is —C (═O) OR ₃ or a phenyl group, R ₃ is —CH ₃ , —CH ₂ CH (CH ₃ ) ₂ , -C (CH ₃ ) ₃ , and-(CH ₂ ) _m Any structure selected from the group of CH ₃ (m represents an integer of 1 to 17. n represents an integer). Thereby, various monomers can be selected as a raw material than the condensate of dimethylsiloxane, the ring-opening polymer of epsilon -caprolactone, the addition polymer of alcohol, and alkylene oxide, etc., and it becomes easy to control the physical property of a cured film. In this case, the physical properties of the cured film can be more easily controlled by combining two or more types of monomers having an unsaturated double bond as a raw material.

80: 20-40: The weight ratio of the said (A) component and (B) component makes it excellent in the outstanding workability and hard coat property of the cured active energy ray hardening-type resin hardened | cured material which are the final products, a low adhesiveness, and the optical characteristic. It is preferable that it is 60. By setting it as this weight ratio, the handling property of a dry film and the physical property of a cured film can be adjusted. That is, if the ratio of the component (A) is too high, the hard coat property is improved, but the workability and adhesion are poor, and if the ratio of the component (B) is too high, the adhesion is good and the handling properties of the dry film are improved, but the hard coat property of the cured film is improved. Is lowered.

As a radical polymerization initiator used when copolymerizing the said (A) component and (B) component, a well-known thing can be used without a limitation. Specifically, For example, inorganic peroxides, such as hydrogen peroxide, ammonium persulfate, potassium persulfate, organic peroxides, such as benzoyl peroxide, dicumyl peroxide, lauryl peroxide, 2, 2'- azobisisobutyronitrile And azo compounds such as dimethyl-2 and 2'-azobisisobutyrate. These may be used individually by 1 type, or may mix and use 2 or more types. In addition, it is preferable that the usage-amount of a radical polymerization initiator is about 0.01-8 weight part with respect to 100 weight part of prepolymerization components. Moreover, you may use a chain transfer agent etc. as needed.

As a chain transfer agent, n-lauryl mercaptan, n-dodecyl mercaptan, 2-mercaptobenzothiazole, bromotrichloromethane, etc. are mentioned, for example. These may be used individually by 1 type, or may mix and use 2 or more types. It is preferable that the usage-amount of a chain transfer agent is about 0.01-5 weight part with respect to 100 weight part of prepolymerization components to be used.

Thus, (C) component is made to react the copolymer (A / B copolymer) of (A) component and (B) component obtained to make active energy ray hardening resin. As the component (C), various known ones can be used without particular limitation. Specifically, (alpha), (beta)-unsaturated monocarboxylic acid, (meth) acrylic acid dimer, such as (meth) acrylic acid, is mentioned. (Meth) acrylic acid is preferable from the viewpoint of the photopolymerization reactivity of the active energy ray hardening-type resin obtained among these, and the hard coat property of hardened | cured material.

Reaction of the said A / B copolymer and (C) component is reaction which the epoxy group of (A) component ring-opens, and (C) component adds. The reaction method is not particularly limited, and a known method can be adopted. Usually, A / B copolymer is mixed with (C) component, and it is performed by heating to 80-120 degreeC in presence of various catalysts as needed.

It is preferable to mix | blend (C) component with respect to the number of epoxy groups of the said A / B copolymer so that a carboxyl group may become the same number. When the number of carboxyl groups is less than the number of epoxy groups, crosslinking of the epoxy groups occurs, which causes thickening. Moreover, (C) component generally has high skin irritation. Therefore, when carboxyl group number is mix | blended excessively more than epoxy group number, (C) component which has an unreacted carboxyl group will be in the state which exists in a product, and is unpreferable from the point of handling.

Examples of the catalysts include, for example, alkaline catalysts, pyridine, pyrrole, triethylamine, diethylamine, amines such as dibutylamine and ammonia, phosphines such as tributylphosphine and triphenylphosphine, and an acid catalyst. Examples thereof include metal alkoxide compounds such as copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, tetrabutoxytrititanium, Lewis acids such as aluminum chloride, organic tin compounds such as dibutyltin dilaurate, and the like. Can be mentioned. Although the usage-amount of a catalyst is not specifically limited, It is preferable to set it as about 0.01-5 weight part normally with respect to 100 weight part of total weights of an A / B copolymer and (C) component.

In reaction of the said A / B copolymer and (C) component, you may use a polymerization inhibitor as needed.

Metoquinone, hydroquinone, trimethylhydroquinone, N-nitrosophenyl hydroxylamine, etc. are mentioned as said polymerization inhibitor. Although the usage-amount of a polymerization inhibitor is not specifically limited, Usually, about 1 weight part or less with respect to 100 weight part of total weights of an A / B copolymer and (C) component, in order not to adversely affect the reaction hardenability of obtained resin. It is desirable to. Moreover, in order to prevent superposition | polymerization, you may blow air into a reaction system.

As a solvent used in the copolymerization reaction of (A) component and (B) component, and the reaction of A / B copolymer and (C) component, if it is the organic solvent in which each component is dissolved, a well-known thing can be used. . Specific examples include alcohols such as propanol and butanol; lower ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and benzene; butyl acetate, ethyl acetate, chloroform, dimethylformamide, and the like. . These may be used individually by 1 type, or may mix and use 2 or more types. In each reaction step, if the reaction temperature is set high, the reaction can be efficiently carried out in a short time. Therefore, although the boiling point is high, the active energy ray-curable hard coat agent has good drying properties. When it is a methyl isobutyl ketone and butyl acetate, since reaction temperature can be set high and drying property is favorable, it is preferable.

The active energy ray-curable resin of the present invention thus obtained has two sites, one site of an unsaturated double bond group crosslinked by active energy ray irradiation, and one site of side chains having no crosslinkable reactor. Since it combines, hard coatability and workability can be made compatible. Moreover, by setting it as the side chain of a specific molecular weight, the dry film surface can be made into low adhesiveness.

The active energy ray-curable resin of the present invention thus obtained has a weight average molecular weight (polystyrene equivalent value by GPC) of about 10,000 to 100,000, and can be treated as a mixed liquid containing an organic solvent. When the weight average molecular weight is less than 10,000, the elongation of the cured film tends to be lowered, and workability is impaired. On the other hand, when it exceeds 100,000, compatibility with an organic solvent will worsen, and it will become impossible to manufacture stable high quality.

It can also be set as the active energy ray hardening-type hard coat agent containing the active energy ray curable resin of this invention and a photoinitiator, and this is also one of this invention. It can also be set as the active energy ray hardening-type hard-coat agent which further contains a polyfunctional (meth) acrylate, and this is also one of this invention. By using polyfunctional (meth) acrylate, the processability and hard coat property of a hard coat agent can be adjusted. Moreover, the active energy ray hardening-type hard coat agent of this invention can also mix | blend an additive. By mix | blending an additive, it can be set as the hard coat agent which can provide the functionality of the improvement of the smoothness of an application | coating surface, antifouling property, and antistatic property.

As said additive, you may contain antioxidant, a ultraviolet absorber, a light stabilizer, an antifoamer, a surface regulator, an antifouling agent, a pigment, an antistatic agent, a metal oxide fine particle dispersion etc. according to the objective.

It is preferable that the polyfunctional (meth) acrylate contained in the hard coat agent of this invention is a composition ratio of 5 to 80 weight% in a resin composition. Thereby, it can use in the range which does not deviate from the coexistence of the hardness and elongation of a cured film.

As said polyfunctional (meth) acrylate, trimethylol propane tri (meth) acrylate, trimethylol propane ethoxy tri (meth) acrylate, glycerin ethoxy tri (meth) acrylate, glycerin propoxy (meth) acryl Ethoxylated isocyanuric acid tri (meth) acrylate, ε-caprolactone modified tris (2- (meth) acryloxyethyl) isocyanurate, pentaerythritol tri / tetra (meth) acrylate, penta Erythritol ethoxytri / tetra (meth) acrylate, pentaerythritol propoxytrityl / tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ε -(Meth) acryl containing acrylic monomer (1), such as caprolactone modified dipentaerythritol hexa (meth) acrylate, a polyhydric isocyanate compound, and a hydroxyl group Urethane obtained by making hydroxyl-containing (meth) acrylate react with the terminal isocyanate group containing compound obtained by making the urethane (meth) acrylate (2) obtained by reaction of a nitrate compound, and the compound containing polyhydric isocyanate and 2 or more hydroxyl groups react. Epoxy (meth) acrylate (3) obtained by adding (meth) acrylic acid to (meth) acrylate (2) 'and an epoxy group is mentioned. Preferably, it is urethane (meth) acrylate (2) * (2) 'and epoxy (meth) acrylate (3). In addition, you may mix these individually or in combination of 2 or more types, respectively. The use ratio of each polyfunctional (meth) acrylate component in the case of using 2 or more types is not specifically limited.

You may mix | blend the hard coat agent of this invention with an inorganic filler for the purpose of improving abrasion resistance. As the inorganic filler, known ones such as silica and metal oxide fine particles can be used without limitation. For example, titanium oxide, aluminum oxide, antimony oxide, tin oxide, zirconium oxide, zinc oxide, cerium oxide, indium oxide, etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more types. Of these, silica, titanium oxide, aluminum oxide, zirconium oxide, and zinc oxide are preferred because the commercial product range is faithful, readily available, and inexpensive.

It is preferable to use the thing controlled by the average particle diameter of the said inorganic filler to 200 nm or less (by laser diffraction and scattering method). When the average particle diameter exceeds 200 nm, whitening of the cured film is likely to occur, and there is a risk of damaging optical properties such as haze and transmission efficiency. Moreover, you may mix | blend various additives, such as a leveling agent, an antifoamer, a slip agent, and a photosensitizer, as needed.

When hardening | curing the hard coat agent of this invention with an ultraviolet-ray, a photoinitiator can be used. As a photoinitiator, as long as it can decompose | disassemble by ultraviolet-ray, generate | occur | produce a radical, and can superpose | polymerize, a well-known thing can be used. Specifically, for example, 2-, 2-dimethoxy- 1, 2-diphenyl ethane- 1-one, 1-cyclohexyl phenyl ketone, 2-hydroxy- 2-methyl- 1- phenyl- propane- 1- On, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-methyl-1- [4- (methylthio) phenyl 2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl)- Phenyl phosphine oxide, 2, 4, 6- trimethyl benzoyl- diphenyl- phosphine oxide, 4-methylbenzo phenone, etc. are mentioned, It can obtain easily from Chiba Japan Co., Ltd. etc. These can be used individually by 1 type or in combination of 2 or more types. It is preferable that the usage-amount of a photoinitiator shall be about 0.1-10 weight part with respect to 100 weight part of active energy ray curable resin compositions.

Moreover, the cured film obtained by hardening | curing by irradiating an active energy ray to the said active energy ray hardening-type hard coat agent is also one of this invention. When the cured film of this invention is used, it can be used as a decorative film which made workability and hard coat property compatible.

Examples of the active energy rays include light (rays such as ultraviolet rays), electron beams, X rays, α rays, β rays, γ rays, neutron rays, and the like. In general, light and electron beams are preferred because they are widely used.

The decorative film on which the cured film is laminated is also one of the present invention. This in-mold decorative film can cope with the design with the deep shape which could not be applied because of the crack of a hard-coat layer so far, and can give the hard-coat property equivalent to the conventional one to the surface of a molded article. . The method can be applied without particular limitation as long as film bonding and injection molding are simultaneously performed in a mold, and can be used for in-mold decorating, label bonding molding, in-molding molding, film insert molding and the like.

There is no restriction | limiting in particular as a base material of the said decorative film, For example, plastics (polycarbonate, polymethylmethacrylate, polystyrene, polyester, polyolefin, an epoxy resin, a melamine resin, a triacetyl cellulose resin, an ABS resin, an AS resin, Norbornene-based resins).

As a method of laminating | stacking a hard-coat layer on the said decorative film, after apply | coating and drying by a well-known method, it performs by irradiating and hardening an active energy ray. Examples of the coating method of the hard coat agent include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, and the like. In addition, an application amount is not specifically limited, Usually, the weight after drying is 0.1-20 g / m <^2> , Preferably it is the range which becomes 0.5-10 g / m <^2> .

The present invention is also a plastic injection molded article using the decorative film. Conventionally, due to the problem of cracking of the hard coat layer, there has been a compromise on the hard coat property of the plastic injection-molded article or the design is limited. However, when the decorative film of the present invention is used, it is possible to cope with complex design and to scratch the surface A difficult plastic injection molded product can be obtained, and it can be used for a case of an electric device such as a mobile phone terminal or a PC, a part of an interior trim or an exterior cover in a car.

Example

Although an Example and a comparative example are given to the following and this invention is concretely demonstrated to it, this invention is not limited to each of these examples. In addition, all parts and% in each case are a basis of weight unless there is particular notice.

<Synthesis example 1 of (B) component>

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet and a dropping funnel, 9.5 parts of methyl methacrylate (hereinafter MMA), 0.8 parts of mercaptopropionic acid, 0.8 parts of butyl acetate, 48.1 parts of azobisisobutyronitrile (hereinafter, 0.5 part of AIBN) was put and stirred, and after heating up to 90 degreeC under nitrogen stream, it dripped for 2 hours from the dropping funnel which previously put MMA # 38.0 parts and AIBN * 1.5 part, and kept 90 degreeC 5 hours. Thereafter, 0.5 parts of AIBN was added thereto, and the resultant was kept warm for 1 hour, and then heated up to 120 ° C., then cooled to room temperature after 2 hours warming. MMA macromonomer solution containing 50% of solid content of one-terminal methacryloyl group was added by removing the dropping funnel, changing the nitrogen inlet to an air bubbler, stirring while bubbling air, raising the temperature to 110 ° C, and keeping it for 9 hours. Got. In addition, the weight average molecular weight (polystyrene conversion value by GPC) was 4,600. A weight average molecular weight shows the value measured by connecting two gel permeation chromatography (The Toso Corporation make, a brand name "HLC-8220", a column: The Tosoh Corporation make, and a brand name "TSKgel 'superHZ2000") in series.

<Synthesis example 2 of (B) component>

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel, 11.8 parts of MMA, 0.2 parts of 2-mercaptoethanol, 39.7 parts of butyl acetate, and 0.5 parts of AIBN: 0.5 parts were stirred, and the mixture was heated to 90 ° C under nitrogen flow. After heating up, it was dripped over 2 hours from the dropping funnel which put 47.3 parts of MMA's and 0.4 parts of AIBNs previously, and after keeping at 90 degreeC for 5 hours, after adding 0.5 parts of AIBNs and keeping for 1 hour, it heated up at 120 degreeC and kept warm for 2 hours. . After cooling to room temperature, 0.4 parts of 2-isocyanate ethyl acrylate # 0.03, octyl titanate # 0.03 part, and metoquinone # 0.1 part were added, and 80 ° C 6 hours of warming was carried out, whereby MMA macromolecule containing 60% of solid content of one end methacryloyl group was contained. Monomer solution was obtained. In addition, the weight average molecular weight (polystyrene conversion value by GPC) was 22,000.

<Synthesis example 3 of (B) component>

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel, 8.1 parts of MMA, 6.3 parts of 2-mercaptoethanol, 49.7 parts of butyl acetate, and 0.1 parts of AIBN were added thereto, followed by stirring. After heating up, it was dripped over 2 hours from the dropping funnel which previously put MMA # 24.1 parts and 0.3 parts of AIBN, and after keeping at 90 degreeC for 5 hours, after adding 0.5 parts of AIBN and keeping it for 1 hour, it heated up at 120 degreeC and kept warm for 2 hours. . Thereafter, the mixture was cooled to room temperature, 11.3 parts of 2-isocyanate ethyl acrylate, 0.02 part of octylic acid tin tin, and 0.1 part of methoquinone were added thereto, and the resultant was kept at 80 ° C for 6 hours, whereby MMA macromolecule containing one end methacryloyl group having a solid content of 50% was added. Monomer solution was obtained. In addition, the weight average molecular weight (polystyrene conversion value by GPC) was 700.

&Lt; Example 1 &gt;

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet and a dropping funnel, GMA'3.3 parts as component (A), 9.8 parts MMA macromonomer in Synthesis Example 1 as component (B) and methyl isobutyl ketone (hereinafter MIBK) 13.1 parts and 0.3 parts of AIBN's were added and stirred, and the temperature was raised to 110 ° C under a nitrogen stream, followed by dropping funnel in which a mixed solution in which AIBN's 1.0 parts were dissolved in GMA # 9.8 parts and 29.5 parts of MMA macromonomer # 2 in Synthesis Example 1 was added. After dropping over time, the mixture was allowed to react for 5 hours, and then 0.2 parts of AIBN was added thereto, followed by warming for 1 hour, heating at 116 ° C, and warming for 3 hours, thereby yielding a copolymer having a branched structure of weight ratio (A) :( B) = 40: 60. Got. Thereafter, after cooling to room temperature, 6.7 parts of acrylic acid (having the same number of carboxyl groups as the number of epoxy groups in the copolymer), 0.3 parts of triphenylphosphine, 0.1 part of metoquinones, and 26.2 parts of MIBK # 26.2 parts were added as a dropping funnel. Was removed, the nitrogen inlet was changed to an air bubble device, stirred while bubbling air, and reacted at 110 ° C. for 6 hours to obtain an active energy ray-curable resin having a branched structure. The weight average molecular weight (polystyrene conversion value by GPC) was 32,000, and solid content was 40%. 2 parts of photoinitiators (brand name "Acucure 184" BASF) were mix | blended with respect to 100 parts of obtained resin solution # 100 parts, and it was set as the hard coat agent.

<Example 2>

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel, (A) component GMA x 3.9 parts, (B) component MMA macromonomer 7.9 parts, MIBK x 15.7 parts, and AIBN as components (B) 0.3 parts was added and stirred, and the temperature was raised to 110 ° C. under a nitrogen stream, followed by dropping for 2 hours from a dropping funnel in which a mixed solution obtained by dissolving 1.0 parts of AIBN was previously added to 11.8 parts of GMA # 1 and 23.6 parts of MMA macromonomer # 2 in Synthesis Example 1, followed by dropwise addition. After the reaction, 0.2 parts of AIBN was added, and the mixture was kept for 1 hour, heated to 116 ° C, and kept for 3 hours to obtain a copolymer having a branched structure having a weight ratio (A) :( B) = 50:50. Thereafter, after cooling to room temperature, 8.0 parts of acrylic acid (having the same number of carboxyl groups as the number of epoxy groups in the copolymer), 0.2 parts of triphenylphosphine, 0.1 part of metoquinone # 0.1 and MIBK # 27.5 parts were added as a dropping funnel. Was removed, the nitrogen inlet was changed to an air bubble device, stirred while bubbling air, and reacted at 110 ° C. for 6 hours to obtain an active energy ray-curable resin having a branched structure. The weight average molecular weight (polystyrene conversion value by GPC) was 28,000, and solid content was 40%. 2 parts of Acucure 184 were mix | blended with respect to obtained resin solution # 100 part, and it was set as the hard coat agent.

<Example 3>

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel, GMA) 5.1 parts as (A) component, MMA macromonomer 4.4 parts of Synthesis Example 1 as component (B), MIBK 20.4 parts, and AIBN 0.3 parts was added and stirred, and after heating up to 110 degreeC under nitrogen stream, it was dripped over 2 hours from the dropping funnel which mixed the mixture liquid which melt | dissolved AIBN 0.9 parts in GMA # 15.3part and MMA macromonomer # 13.1 part of the synthesis example 1, and then dripped for 5 hours. After the reaction, 0.2 parts of AIBN was added, and the mixture was kept for 1 hour, heated to 116 ° C, and kept for 3 hours to obtain a copolymer having a branched structure having a weight ratio (A) :( B) = 70:30. After cooling to room temperature thereafter, 10.4 parts of acrylic acid (having the same number of carboxyl groups as the number of epoxy groups of the copolymer), 0.3 parts of triphenylphosphine, 0.1 part of metoquinone # 0.1, and MIBK # 29.8 parts were added as a dropping funnel. Was removed, the nitrogen inlet was changed to an air bubble device, stirred while bubbling air, and reacted at 110 ° C. for 6 hours to obtain an active energy ray-curable resin having a branched structure. The weight average molecular weight (polystyrene conversion value by GPC) was 14,000, and solid content was 40%. 2 parts of Acucure 184 were mix | blended with respect to obtained resin solution # 100 part, and it was set as the hard coat agent.

<Example 4>

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet and a dropping funnel, 4.0 parts of GMA as component (A), 7.9 parts of MMA macromonomer of Synthesis Example 1 as component (B), MIBK-15.8 parts, and AIBN 0.2 parts was added and stirred, and the temperature was raised to 80 ° C. under a stream of nitrogen, followed by 2 hours from a dropping funnel in which a mixed solution obtained by dissolving 0.5 parts of AIBN was previously added to GMA # 11.9 parts and MMA macromonomer # 23.8 parts in Synthesis Example 1, followed by 5 hours After reacting, 0.1 part of AIBN was added, it was further kept warm for 1 hour, and it heated up at 116 degreeC, and kept for 3 hours, and obtained the copolymer which has a branched structure of weight ratio (A) :( B) = 50: 50. Thereafter, after cooling to room temperature, 8.0 parts of acrylic acid (having the same number of carboxyl groups as the number of epoxy groups of the copolymer), 0.3 parts of triphenylphosphine, 0.1 part of metoquinone # 0.1, and 27.7 parts of MIBK were added as a dropping funnel. Was removed, the nitrogen inlet was changed to an air bubble device, stirred while bubbling air, and reacted at 110 ° C. for 6 hours to obtain an active energy ray-curable resin having a branched structure. The weight average molecular weight (polystyrene conversion value by GPC) was 85,000, and solid content was 40%. 2 parts of Acucure 184 were mix | blended with respect to obtained resin solution # 100 part, and it was set as the hard coat agent.

<Example 5>

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel, 3.9 parts of GMA '3.9 parts as component (A) and 3.9 parts of styrene macromonomer (trade name "AS-6" TOA Synthetic Co., Ltd.) as components (B). After stirring, add 15.7 parts of MIBK and 0.3 parts of AIBN, and add dropwise funnel containing 11.8 parts of AS-6 and 1.0 parts of AIBN 부 에 to 15.7 parts of MIBK, add dropwise funnel, and react for 5 hours, and then add 0.2 parts of AIBN. Moreover, it maintained for 1 hour, heated up at 116 degreeC, and kept for 3 hours, and obtained the copolymer which has a branched structure of weight ratio (A) :( B) = 50: 50. Thereafter, after cooling to room temperature, 8.0 parts of acrylic acid (having the same number of carboxyl groups and the same number of carboxyl groups) of acrylic acid, 0.3 parts of triphenylphosphine, 0.1 parts of metoquinones, and 27.3 parts of MIBK's were added to the dropping funnel. Was removed, the nitrogen inlet was changed to an air bubble device, stirred while bubbling air, and reacted at 110 ° C. for 6 hours to obtain an active energy ray-curable resin having a branched structure. The weight average molecular weight (polystyrene conversion value by GPC) was 24,000 and solid content 40%. 2 parts of Acucure 184 were mix | blended with respect to obtained resin solution # 100 part, and it was set as the hard coat agent.

<Example 6>

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel, GMA'3.9 parts as (A) component and isobutyl methacrylate macromonomer (brand name "AW-6S") as (B) component Synthetic Co., Ltd.) 8.0 parts, MIBK # 22.5 parts, and 0.3 parts of AIBN were added and stirred, and the temperature was raised to 110 ° C under a nitrogen stream, and then from a dropping funnel in which a mixed solution obtained by dissolving AIBN 1.0 parts was previously dissolved in GMA # 11.8 parts and AW-6S # 24.0 parts. After dripping for 2 hours, the mixture was allowed to react for 5 hours, and then 0.2 parts of AIBN was added, followed by warming for 1 hour, heating at 116 ° C, and warming for 3 hours, thereby allowing air having a branching structure with a weight ratio (A) :( B) = 50:50. The coalescence was obtained. Thereafter, after cooling to room temperature, 8.0 parts of acrylic acid (having the same number of carboxyl groups as the number of epoxy groups of the copolymer), 0.2 parts of triphenylphosphine, 0.1 part of metoquinones, and 20.5 parts of MIBK # 20.5 parts were added as a dropping funnel. Was removed, the nitrogen inlet was changed to an air bubble device, stirred while bubbling air, and reacted at 110 ° C. for 6 hours to obtain an active energy ray-curable resin having a branched structure. The weight average molecular weight (polystyrene conversion value by GPC) was 26,000 and solid content 40%. 2 parts of Acucure 184 were mix | blended with respect to obtained resin solution # 100 part, and it was set as the hard coat agent.

<Example 7>

Into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel, MIBK 15.1 parts were added and heated to 90 ° C. under nitrogen stream while stirring, and beforehand, GMA 18.1 parts, (B) component as (A) component. To the MMA macromonomer, 12.0 parts of Toa Synthetic Co., Ltd. product name "AA-6", 15.1 parts of MIBK # 15.1 parts, and AIBN # 1.2 parts were added dropwise over 2 hours from a dropping funnel, followed by reaction for 5 hours, and then AIBN 0.6 parts were added. The copolymer of weight ratio (A) :( B) = 60: 40 was obtained by heat-retaining for time, heating up at 116 degreeC, and keeping for 3 hours. Thereafter, after cooling to room temperature, 9.2 parts of acrylic acid (having the same number of carboxyl groups as the number of epoxy groups of the copolymer), 0.3 parts of triphenylphosphine, 0.1 part of metoquinone #, and 28 parts of MIBK # 28.4 were added into the dropping funnel. Was removed, the nitrogen inlet was changed to an air bubble device, stirred while bubbling air, and reacted at 110 ° C. for 6 hours to obtain an active energy ray-curable resin. The weight average molecular weight was 18,000 and solid content was 40%. 2 parts of Acucure 184 were mix | blended with respect to obtained resin solution # 100 part, and it was set as the hard coat agent.

&Lt; Comparative Example 1 &

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel, 6.6 parts of GMA's, 26.2 parts of MIBK's and 0.3 parts of AIBN's were added thereto, and the mixture was stirred. It was dripped for 2 hours from the dropping funnel which mixed the mixed solution which melt | dissolved AIBN_0.8 part in 2 hours, and after making it react for 5 hours, AIBN_0.1 part was added, it warmed for 1 hour, it heated up at 116 degreeC, and kept for 3 hours, and obtained the GMA homopolymer. Thereafter, after cooling to room temperature, 13.3 parts of acrylic acid (having the same number of carboxyl groups as the number of epoxy groups of the copolymer), 0.3 parts of triphenylphosphine, 0.1 part of metoquinones, and 3.7 parts of MIBK were removed, and the dropping funnel was removed to remove nitrogen inlet. The mixture was changed to an air bubbler, stirred while bubbling air, and reacted at 110 ° C. for 6 hours to obtain an epoxy acrylate. The weight average molecular weight (polystyrene conversion value by GPC) was 20,000, and solid content was 40%. 2 parts of Acucure 184 were mix | blended with respect to obtained resin solution # 100 part, and it was set as the hard coat agent.

<Comparative Example 2>

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet and a dropping funnel, GMA G3.9 parts, MMA 3.9 parts, MIBK 31.5 parts, and AIBN 교반 0.3 parts were added and stirred, and the temperature was raised to 110 ° C under nitrogen airflow. It was dripped for 2 hours from the dropping funnel which mixed the mixture liquid which melt | dissolved AIBN 0.9 part in GMA'11.8 parts and MMA'11.8 parts previously, and made it react for 5 hours, Then, 0.2 parts of AIBN was added, it warmed for 1 hour, it heated up at 116 degreeC, and kept warm for 3 hours. Thus, a GMA / MMA copolymer was obtained. Thereafter, after cooling to room temperature, 8.0 parts of acrylic acid (having the same number of carboxyl groups as the number of epoxy groups of the GMA / MMA copolymer), 0.3 parts of triphenylphosphine, 0.1 part of metoquinones, and 27.3 parts of MIBK's were added, and the dropping funnel was removed. The inside of the nitrogen inlet was turned into an air bubbler, stirred while bubbling air, and reacted at 110 ° C. for 6 hours to obtain an active energy ray-curable resin. The weight average molecular weight (polystyrene conversion value by GPC) was 15,000, and solid content was 40%. 2 parts of Acucure 184 were mix | blended with respect to obtained resin solution # 100 part, and it was set as the hard coat agent.

&Lt; Comparative Example 3 &

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel, GMA x 3.9 parts as component (A), 6.6 parts MMA macromonomer of Synthesis Example 2 as component (B), MIBK # 15.7 part, and AIBN 0.3 parts was added and stirred, and after heating up to 110 degreeC under nitrogen stream, it was dripped for 2 hours from the dropping funnel which mixed the mixture liquid which melt | dissolved AIBN # 1.0 part previously in 11.8 parts of GMA # 19.6 parts and MMA macromonomer # 19.6 of the synthesis example 2, and then dripped for 5 hours. After the reaction, 0.2 parts of AIBN was added, and the mixture was kept for 1 hour, heated to 116 ° C, and kept for 3 hours to obtain a copolymer having a branched structure having a weight ratio (A) :( B) = 50:50. Thereafter, after cooling to room temperature, 8.0 parts of acrylic acid (having the same number of carboxyl groups as the number of epoxy groups of the copolymer), 0.2 parts of triphenylphosphine, 0.1 part of metoquinone # 0.1, and MIBK # 32.7 part were added as a dropping funnel. Was removed, the nitrogen inlet was changed to an air bubble device, stirred while bubbling air, and reacted at 110 ° C. for 6 hours to obtain an active energy ray-curable resin having a branched structure. The weight average molecular weight (polystyrene conversion value by GPC) was 52,000, and solid content was 40%. 2 parts of Acucure 184 were mix | blended with respect to obtained resin solution # 100 part, and it was set as the hard coat agent.

&Lt; Comparative Example 4 &

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel, (A) component GMA x 3.9 parts, (B) component MMA macromonomer 7.9 parts of Synthesis Example 3, MIBK x 15.7 parts, and AIBN 0.3 parts was added and stirred, and after heating up to 110 degreeC under nitrogen stream, it was dripped for 2 hours from the dropping funnel which mixed the mixture liquid which melt | dissolved AIBN # 1.0 part previously in 11.8 parts of GMA # 1, and 23.6 parts of MMA macromonomer # 2 of the synthesis example 3, and then dripped for 5 hours. After the reaction, 0.2 parts of AIBN was added, and the mixture was kept for 1 hour, heated to 116 ° C, and kept for 3 hours to obtain a copolymer having a branched structure having a weight ratio (A) :( B) = 50:50. Thereafter, after cooling to room temperature, 8.0 parts of acrylic acid (having the same number of carboxyl groups as the number of epoxy groups in the copolymer), 0.2 parts of triphenylphosphine, 0.1 part of metoquinone # 0.1 and MIBK # 27.5 parts were added as a dropping funnel. Was removed, the nitrogen inlet was changed to an air bubble device, stirred while bubbling air, and reacted at 110 ° C. for 6 hours to obtain an active energy ray-curable resin having a branched structure. The weight average molecular weight (polystyrene conversion value by GPC) was 18,000, and solid content was 40%. 2 parts of Acucure 184 were mix | blended with respect to obtained resin solution # 100 part, and it was set as the hard coat agent.

<Comparative Example 5>

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel, GMA'4.0 parts as (A) component, MMA macromonomer's 8.0 parts of Synthesis Example 1 as component (B), MIBK'15.9 parts, and AIBN 0.04 parts were added and stirred, and the temperature was raised to 110 ° C. under a nitrogen stream, followed by dropping for 2 hours from a dropping funnel in which a mixed solution obtained by dissolving AIBN 0.1 parts was dissolved in GMA # 11.9 parts and MMA macromonomer # 23.8 parts in Synthesis Example 1, and then 5 hours. After reacting, 0.1 part of AIBN was added, it was further kept warm for 1 hour, and it heated up at 116 degreeC, and kept for 3 hours, and obtained the copolymer which has a branched structure of weight ratio (A) :( B) = 50: 50. Thereafter, after cooling to room temperature, 8.1 parts of acrylic acid (having the same number of carboxyl groups as the number of epoxy groups of the copolymer), 0.2 parts of triphenylphosphine, 0.1 part of metoquinone # 0.1 and MIBK # 27.7 part were added as a dropping funnel. Was removed, the nitrogen inlet was changed to an air bubble device, stirred while bubbling air, heated to 110 ° C, and kept warm, and gelated after 1 hour.

&Lt; Comparative Example 6 &gt;

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel, GMA '5.0 parts as (A) component, 4.3 parts of MMA macromonomer in Synthesis Example 1 as component (B), n-octyl mercaptan # 0.04 Part A, MIBK # 20.0 parts and AIBN # 0.7 part were added and stirred, and the temperature was raised to 116 ° C under a nitrogen stream, and in advance, GMA # 14.9 parts, MMA macromonomer # 12.8 parts and n-octyl mercaptan 0.1 part AIBN # 2.2 parts in advance After dropping for 2 hours from the dropping funnel containing the dissolved liquid mixture, the mixture was allowed to react for 5 hours, and then 0.4 parts of AIBN was added thereto, followed by warming for 4 hours. Got it. Thereafter, after cooling to room temperature, 10.2 parts of acrylic acid (having the same number of carboxyl groups as the number of epoxy groups of the copolymer), 0.2 parts of triphenylphosphine, 0.1 part of metoquinones, and MIBK # 29.2 parts were added as a dropping funnel. Was removed, the nitrogen inlet was changed to an air bubble device, stirred while bubbling air, and reacted at 110 ° C. for 6 hours to obtain an active energy ray-curable resin having a branched structure. The weight average molecular weight (polystyrene conversion value by GPC) was 8,000, and solid content was 40%. 2 parts of Acucure 184 were mix | blended with respect to obtained resin solution # 100 part, and it was set as the hard coat agent.

&Lt; Comparative Example 7 &

Into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel, MIBK 27.2 parts were added and stirred to raise the temperature to 90 ° C. under nitrogen stream while stirring, and beforehand, GMA 10.2 parts as the component (A) and (B) component. To the mixed solution obtained by dissolving 47.6 parts of MMA macromonomer # 4 and 1.4 parts of AIBN obtained in Synthesis Example 1 was added dropwise over 2 hours from a dropping funnel, and then reacted for 5 hours. Then, 0.6 parts of AIBN was added thereto, followed by warming for 1 hour, followed by heating to 116 ° C. The copolymer of weight ratio (A) :( B) = 30: 70 was obtained by keeping warm for 3 hours. After cooling to room temperature thereafter, 5.2 parts of acrylic acid (having the same number of carboxyl groups as the number of epoxy groups of the copolymer), 0.2 parts of triphenylphosphine, 0.1 part of metoquinone # 0.1, and MIBK 7.6 parts were added as a dropping funnel. Was removed, the nitrogen inlet was changed to an air bubble device, stirred while bubbling air, and reacted at 110 ° C. for 6 hours to obtain an active energy ray-curable resin having a branched structure. The weight average molecular weight was 30,000, and the solid content was 40%.

&Lt; Comparative Example 8 &gt;

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel, GMA) 4.4 parts as (A) component, 1 part MMA macromonomer of Synthesis Example 1 as component (B), MIBK 27.5 parts, and AIBN 0.2 parts was added and stirred, and after heating up to 110 degreeC under nitrogen stream, it was dripped over 2 hours from the dropping funnel which mixed the solution which melt | dissolved GMA # 13.3part, 3 parts of MMA macromonomer of Synthesis Example 1, and AIBN # 0.6part previously, and dripped for 5 hours. After reacting, 0.1 part of AIBN was added, it was further warmed for 1 hour, and it heated up at 116 degreeC, and was kept for 3 hours, and obtained the copolymer which has a branched structure of weight ratio (A) :( B) = 90: 10. Thereafter, after cooling to room temperature, 20 parts of acrylic acid (having the same number of carboxyl groups as the number of epoxy groups of the copolymer), 0.3 parts of triphenylphosphine, 0.1 part of metoquinone # 0.1 and MIBK # 29.6 parts were added as a dropping funnel. Was removed, the nitrogen inlet was changed to an air bubble device, stirred while bubbling air, and reacted at 110 ° C. for 6 hours to obtain an active energy ray-curable resin having a branched structure. The weight average molecular weight (polystyrene conversion value by GPC) was 10,000, and solid content was 40%. 2 parts of Acucure 184 were mix | blended with respect to obtained resin solution # 100 part, and it was set as the hard coat agent.

<Adjustment made of hard coat>

50 parts of the hard coat agent obtained in Example 2 and 50 parts of the hard coat agent obtained in Comparative Example 1 were mixed to prepare a hard coat agent composed of an active energy ray-curable resin having a branched structure and an epoxy acrylate as Example 8. It was.

(Manufacture 1 of evaluation coating film)

The hard coat agent of each Example and the comparative example was made into the easily coated surface of 188 micrometer-thick one side | surface adhesive bonding polyethylene terephthalate film (brand name "A4100" Toyo Spinning Co., Ltd.). It applied at 12, dried at 80 degreeC for 1 minute, removed the solvent powder, the dry coating film of about 5 micrometers in thickness was produced, and the adhesiveness was evaluated.

(Evaluation of adhesiveness)

Adhesiveness was evaluated as an index of blocking resistance, and the test shown next was done. Preparation of Evaluation Coating Film The dry coating film of Preparation 1 was cut into a size of 5 × 5 cm, and the polyethylene terephthalate film which was not easily adhesive-treated was bonded to the dry film surface side, put on a glass plate, and a load of 100 g / cm ² was applied for 24 hours. It left still and evaluated adhesiveness by the four steps shown below by the stuck state of a dry film and a polyethylene terephthalate film.

4: not attached at all

3: There is a part which is not affixed, and the part which affixes also peels easily.

2: Although the whole is affixed, it peels easily

1: It sticks whole and is hard to peel off

It judged that evaluation 3 was low adhesiveness and evaluation 4 was more excellent low adhesiveness, and it was said that it had blocking resistance with respect to evaluation 3 or more. On the other hand, evaluation 2 is inferior in adhesiveness, and evaluation 1 can be said to be a state with extremely high adhesiveness, and evaluated the thing of evaluation 2 or less as having no blocking resistance.

(Manufacture 2 of evaluation coating film)

Manufacture of evaluation coating film The dry coating film of manufacture 1 was irradiated with the accumulated light quantity of 300mJ / cm <^{2> with} a high pressure mercury lamp, the cured film was produced, and the coating film physical properties shown below were evaluated.

The cured film manufactured using the hard coat agent of each Example and the comparative example shows the result of having tested the hard coat property and workability by the following item and the evaluation method.

(Evaluation of hard coat property)

Evaluation of hard coat property was performed by carrying out the pencil hardness test according to the test method of JIS-K-5600. Here, pencil hardness F evaluated that the hard coat property was inferior, the pencil hardness H had a hard coat property, and the pencil hardness 2H had the outstanding hard coat property.

(Evaluation of Machinability)

Workability was evaluated by elongation of a cured film. When the elongation is large, it means that the stretching stress applied during injection molding can be flexibly followed, and the cracking of the hard coat layer can be suppressed.

As for elongation, the test piece which cut the cured film into strip shape of length 100mm and width 7mm is set to 50 mm of chuck distances by the chuck in a tensile tester (model number "RTC-1250A" Orientec), and room temperature 25 degreeC, humidity Under a 45% RH environment, a tensile speed of 10 mm / min was applied, and the distance between the chucks was stopped at 55 mm (10% elongation), 60 mm (20% elongation), and 65 mm (30% elongation), respectively. The presence or absence of was observed by eye, and (circle) when there was no crack, and it evaluated by x when a crack generate | occur | produced.

(Measurement of haze)

The active energy ray curable resin of the present invention requires transparency after curing. When transparency is inadequate, the color of design patterns, such as pattern ink which becomes a base, will be impaired. About the transparency of the cured film, the cured film manufactured by the manufacture 2 of evaluation coating film was measured based on JIS-K-7105 using the haze meter "HM-150" (Murakami Institute of Color Technology). It was evaluated that the measured value was less than 0.7 not to impair the designability of the lower limb, and was determined to be "○", and the value of 0.7 or more was judged to be a level that impairs the designability, and was set to "x".

Claims (8)

A macromonomer (B) having a weight average molecular weight of 1,000 to 20,000 having an epoxy group-containing (meth) acrylate-based monomer (A) and an unsaturated double bond at one of the terminals and not containing an epoxy group and a carboxyl group, is weight ratio (A): (B) Activity which is obtained by making (alpha), (beta)-unsaturated carboxylic acid (C) react with the copolymer which has a branched structure obtained by making it react at 80: 20-40: 60, and is characterized by the weight average molecular weight 10,000-100,000. Energy ray curable resin. The method of claim 1,
The macromonomer (B) is a radical copolymer having a radical polymerizable group having a terminal structure represented by General Formula (1).

(Wherein X is a site having a radical polymerizable group, R ₁ is H or CH ₃ , R ₂ is —C (═O) OR ₃ or a phenyl group, R ₃ is —CH ₃ , —CH ₂ CH (CH ₃ ) ₂ , -C (CH ₃ ) ₃ , and-(CH ₂ ) _m Any structure selected from the group of CH ₃ (m represents an integer of 1 to 17. n represents an integer) The active energy ray-curable resin composition of Claim 1 or 2 and a photoinitiator are contained, The active energy ray curable resin composition characterized by the above-mentioned. The method of claim 3,
It further contains a polyfunctional (meth) acrylate, The active-energy-ray-curable resin composition characterized by the above-mentioned. An active energy ray hardening-type hard coat agent containing the active energy ray hardening type resin composition of Claim 3 or 4. The cured film obtained by hardening | curing by irradiating an active energy ray to the active energy ray hardening-type hard-coat agent of Claim 5. The decorative film in which the cured film of Claim 6 was laminated | stacked. The plastic injection molded article using the decorative film of Claim 7.