JP2016074888A - Undercoat agent for plastic with aluminum thin film, plastic with aluminum thin film, plastic film with aluminum thin film, decorated film for in-mold molding, and decorated film for insert molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel undercoat agent which, even when kept a plastic with an aluminum thin film under high temperature and high humidity, does not cause drop in adhesion between the aluminum thin film and a plastic substrate, and does not generate whitened portions or fine transparent portions on a surface of the aluminum thin film.SOLUTION: The undercoat agent for a plastic with an aluminum thin film comprises: a prescribed acrylic copolymer (A) having a glass transition temperature of 0 to 100°C and a hydroxyl equivalent of 0.8 to 3.5 meq/g; an isocyanate composition (B) comprising a reaction product of triisocyanates (b1), and diols and/or water (b2), and having an isocyanate group equivalent of 1 to 10 meq/g; and an epoxy group-containing silicon compound (C) comprising a prescribed epoxy group-containing alkoxysilane (c1) and/or an epoxy group-containing silsesquioxane (c2) formed by subjecting the alkoxysilane to a hydrolysis reaction or a condensation reaction.SELECTED DRAWING: None

Description

  The present invention relates to an undercoat agent used for adhering an aluminum thin film to a plastic substrate, a plastic with an aluminum thin film obtained by using the undercoat agent, a plastic film with an aluminum thin film, and the plastic film as a member. The present invention relates to a decorative film for in-mold molding and insert molding.

  The plastic with an aluminum thin film is one in which a thin film made of aluminum is formed on the surface of a plastic substrate. In particular, an aluminum thin film with a thickness of about several tens of nanometers laminated on a plastic film is awarded as a member of a decorative film for in-mold molding or insert molding. In recent years, it has been used in various electronic products such as mobile phones, audio products, personal computers, automobile interior parts, and the like because it can provide design properties.

  By the way, in order to make an aluminum thin film and a plastic base material contact | adhere, the undercoat agent which has various polymers as a main component is used in many cases.

  For example, Patent Document 1 describes an undercoat agent containing a polyol and a polyisocyanate having a predetermined glass transition temperature and a hydroxyl group equivalent. According to this, the adhesion between a plastic film and an aluminum thin film is good. It will be.

  Patent Document 2 describes an undercoat agent containing an acrylic copolymer having a specific hydroxyl group concentration and a polyisocyanate, each of which comprises a specific alkyl (meth) acrylate and a hydroxyl group-containing (meth) acrylate. And according to this thing, not only the adhesiveness of a plastic film and an aluminum vapor deposition film becomes favorable, but even if it puts this plastic film with an aluminum thin film in a high temperature state, it is supposed that whitening does not arise in an aluminum thin film.

JP 2009-227837 A JP 2011-132521 A

  However, when the plastic with an aluminum thin film obtained using the undercoat agent of Patent Document 1 is placed in a high-temperature and high-humidity state, the adhesion between the plastic substrate and the aluminum thin film is reduced, or a whitened portion is generated in the aluminum thin film There was a problem to do.

  Moreover, when the plastic with an aluminum thin film according to Patent Document 2 is placed in a high-temperature and high-humidity state, as shown in FIG. Was found.

  It is an object of the present invention to provide a novel undercoat agent that does not deteriorate the adhesion between an aluminum thin film and a plastic substrate even under high temperature and high humidity, and that does not cause whitening or omission in the aluminum thin film.

  The present inventor believes that the “missing” is formed of some reaction product of aluminum and water, and is transparent in the visible light region. As shown in FIG. I thought that a hole would appear.

  And as a result of studying means for maintaining adhesion and whitening resistance while eliminating the problem of omission, a predetermined epoxy group-containing silane compound is further added to an undercoat agent containing a predetermined acrylic polyol and polyisocyanate. Thus, it was found that an undercoat agent capable of solving the above-described problems can be obtained.

That is, the present invention is a reaction product of hydroxy group-free alkyl (meth) acrylates (a1) and hydroxy group-containing alkyl (meth) acrylates (a2), having a glass transition temperature of 0 to 100 ° C., and A reaction product comprising an acrylic copolymer (A) having a hydroxyl group equivalent of 0.8 to 3.5 meq / g, a triisocyanate (b1), a diol and / or water (b2) (b2), and an isocyanate group equivalent Is an isocyanate composition (B) in which 1 to 10 meq / g and the general formula (1): X-Si (R ¹ ) _a (OR ² ) _3-a (wherein X is carbon number 1 containing an epoxy group) -8 hydrocarbon group, R ¹ represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, R ² represents a hydrocarbon group having 1 to 8 carbon atoms, and a represents 0 or 1. Epoxy group-containing alkoxy Undercoat agent for plastics with aluminum thin film containing silane (c1) and / or an epoxy group-containing silicon compound (C) composed of an epoxy group-containing silsesquioxane (c2) obtained by subjecting it to a hydrolysis reaction and a condensation reaction , Regarding.

  The present invention also relates to a plastic with an aluminum thin film having a plastic substrate (excluding a plastic film), a layer made of the undercoat agent, and an aluminum thin film layer.

  Moreover, this invention relates also to the plastic film with an aluminum thin film which has a plastic film, the layer which consists of said undercoat agent, and an aluminum thin film layer.

  Moreover, this invention relates also to the decorative film for in-mold shaping | molding which uses the said plastic film with an aluminum thin film as a member, and the decorative film for insert molding.

  The undercoat agent of the present invention is a transparent composition and has a long pot life at room temperature. According to the undercoat agent, the initial adhesion between the aluminum thin film and the plastic substrate (hereinafter also simply referred to as initial adhesion), the adhesion between the aluminum thin film and the plastic substrate under high temperature and high humidity (hereinafter referred to as moisture resistance). As well as whitening resistance and drop resistance of the aluminum thin film surface (hereinafter, also simply referred to as “whitening resistance” and “drop resistance” in order).

  The plastic with an aluminum thin film according to the present invention (except for a film-like one) has good initial adhesion, wet heat resistance, whitening resistance, and slip-out resistance. This can be used for applications such as bottles and caps, mobile phones, audio products, personal computers, and housings for various electronic products such as automobile interior parts.

  The plastic film with an aluminum thin film according to the present invention is also good in initial adhesion, wet heat and heat resistance, whitening resistance, and dropout resistance. In addition to being suitable as a member of a decorative film for in-mold molding or insert molding, this material is suitable as a packaging material such as a gas barrier film, a transparent conductive sheet, a film capacitor, or a member for a display label.

It is a microscope picture (400 times) of the vapor deposition surface of the aluminum vapor deposition PET film which concerns on Example 1, and it turns out that it is extremely smooth and the missing has not arisen. It is a microscope picture (400 times) of the vapor deposition surface of the aluminum vapor deposition PET film which concerns on the comparative example 1, and it turns out that the omission has arisen in the vapor deposition surface.

  The undercoat agent of the present invention comprises a predetermined acrylic copolymer (A) (hereinafter also referred to as component (A)), an isocyanate composition (B) (hereinafter also referred to as component (B)), and an epoxy group-containing silicon compound. It is a composition containing (C) (hereinafter also referred to as component (C)) as an essential component.

  The component (A) includes hydroxy group-free alkyl (meth) acrylates (a1) (hereinafter also referred to as (a1) component) and hydroxy-containing alkyl (meth) acrylates (a2) (hereinafter referred to as (a2) component). It is a copolymer obtained by reacting.

  As the component (a1), various known compounds can be used without particular limitation as long as they are alkyl (meth) acrylates having no hydroxy group in the molecule. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, (meth) acrylic Tert-butyl acid, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexadecyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, icosyl (meth) acrylate, ( Examples thereof include docosyl acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentanyl (meth) acrylate, and isobornyl (meth) acrylate, and these may be used alone or in combination. The above can be used in combination. Among these, the alkyl (meth) acrylate having about 1 to 20 carbon atoms in the alkyl group is preferable because it contributes to the improvement of the slip resistance of the undercoat agent of the present invention. Moreover, physical properties, such as a glass transition temperature of (A) component, can be adjusted by using together (a1) component from which carbon number of an alkyl group differs.

  The component (a2) is a monomer that is essential for the purpose of imparting a hydroxy group to the component (A) and reacting this with the component (B) and the component (C), and has a hydroxy group in the molecule. Any known alkyl (meth) acrylate can be used without particular limitation. Specifically, for example, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-methacrylic acid 3- Hydroxybutyl, 4-hydroxybutyl (meth) acrylate, hydroxycyclohexyl (meth) acrylate, 4- (hydroxymethyl) cyclohexylmethyl (meth) acrylate, 4- (hydroxymethyl) cyclohexylmethyl 2-hydroxypropionate, etc. These may be used alone or in combination of two or more. Among these, those having about 1 to 4 carbon atoms of the hydroxyalkyl group are preferable from the viewpoint of the pot life of the undercoat agent according to the present invention.

  In the present invention, as a constituent monomer of the component (A), a monomer that does not correspond to either the component (a1) or the component (a2) (hereinafter also referred to as the component (a3)) can be used in combination. Specifically, for example, (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, 3-butenoic acid, 4-pentenoic acid, Α, β unsaturated carboxylic acids such as 5-hexenoic acid, maleic acid, crotonic acid, maleic anhydride, fumaric acid and itaconic acid; styrenes such as styrene, α-methylstyrene and t-butylstyrene; Α-olefins such as 4-trimethyl-1-pentene, 3-methyl-1-butene, 3-methyl-1-pentene, 1-hexene, vinylcyclohexane and 2-methylvinylcyclohexane; (meth) allyl alcohol, 4-pentene Insaturation such as -1-ol, 1-methyl-3-buten-1-ol and 5-hexen-1-ol Alcohol; aryl (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate and 4-methylbenzyl (meth) acrylate; dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylamino Dialkylaminoalkyl (meth) acrylates such as ethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, and dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) ) Dialkylaminoalkyl (meth) acrylamids and their salts such as acrylamide and diethylaminopropyl (meth) acrylamide; N, N-dimethyl (meth) acrylamide, Chain transfer monomers such as diacetone (meth) acrylamide, isopropyl (meth) acrylamide, 2- (meth) acrylamide-2-methylpropanesulfonic acid, 2- (meth) acrylamide-2-methylpropanecarboxylic acid and salts thereof Other monofunctional monomers such as vinylamine, aminoethyl (meth) acrylate, allyl mercaptan and glycidyl (meth) acrylate; bis such as methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide and hexamethylene bis (meth) acrylamide (Meth) acrylamide; di (meth) acrylic esters such as ethylene glycol di (meth) acrylic ester and diethylene glycol di (meth) acrylic ester; dibi such as divinyl adipate and divinyl sebacate Bifunctional monomers such as diallyldimethylammonium, diallylphthalate, diallylchlorendate and divinylbenzene; 1,3,5 triacryloylhexahydro-S-triazine, triallyl isocyanurate, triallylamine, triallyl trimellitate And trifunctional monomers such as N, N-diallylacrylamide; tetrafunctional monomers such as tetramethylolmethane tetraacrylate, tetraallyl pyromellitate and N, N, N ′, N′-tetraallyl-1,4 diaminobutane; Examples include acrylonitrile such as acrylonitrile and methacrylonitrile; acrylamide such as acrylamide, methacrylamide, N-methylolacrylamide, and N-methylolmethacrylamide.

When only the component (a1) and the component (a2) are used as the constituent monomer of the component (A), their use ratio is not particularly limited, but is usually as follows.
(A1) component: usually about 45 to 97 mol%, preferably about 65 to 90 mol% (a2) component: usually about 3 to 45 mol%, preferably about 10 to 35 mol%

In addition, when the component (a3) is used in combination with the component (a1) and the component (a2), the use ratio thereof is not particularly limited, but is usually as follows.
(A1) component: usually about 65 to 90 mol%, preferably about 70 to 85 mol% (a2) component: usually about 5 to 35 mol%, preferably about 10 to 30 mol% (a3) component: usually 1 to About 20 mol%, preferably about 1 to 15 mol%

  The component (A) can be produced by various known methods. Specifically, for example, the component (a1) and the component (a2) and, if necessary, the component (a3) are used in the absence of a solvent or in an organic solvent (D) (hereinafter also referred to as component (D)). In general, a copolymerization reaction may be performed for about 1 to 10 hours at about 80 to 180 ° C. in the presence of a radical polymerization initiator.

  Examples of the component (D) include ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aromatic solvents such as toluene and xylene; and low solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol and butyl alcohol. Molecular alcohol solvents; glycol ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and propylene glycol monomethyl ether acetate; ethyl acetate, butyl acetate, methyl cellosolve acetate and cellosolve acetate Ester solvents such as Solvesso # 100 Petroleum solvents such as Sorbesso # 150 (both trade names, manufactured by Exxon); and other solvents such as chloroform and dimethylformamide are used, and the amount used is 10 to 10% by weight of the solid content of the solution containing the component (A). The range is about 50% by weight.

  Examples of the radical polymerization initiator include hydrogen peroxide, ammonium persulfate, potassium persulfate, t-butyl peroxybenzoate, dicumyl peroxide, lauryl peroxide, 2,2′-azobisisobutyronitrile and dimethyl. -2,2'-azobisisobutyrate etc. are mentioned, The usage-amount is the range used as about 0.1 to 2 weight% normally with respect to the total weight of the monomer which comprises (A) component.

  The component (A) thus obtained has a glass transition temperature of 0 to 100 ° C. and a hydroxyl group equivalent of 0.8 to 3.5 meq / g. Since the component (A) is well compatible with the component (B) and the component (C), the undercoat agent of the present invention becomes transparent and can be stored for a long time at room temperature. Moreover, by making such (A) component, (B) component, and (C) component react, the said initial stage adhesiveness, wet heat resistant adhesiveness, whitening resistance, and drop-out resistance become favorable. From this viewpoint, the glass transition temperature of the component (A) is preferably about 25 to 80 ° C., and the hydroxyl group equivalent is preferably about 1 to 2.5 meq / g.

  When the component (a3) is used in combination, the acid value of the component (A) is usually about 0.06 to 0.4 meq / g, preferably 0.09 to 0.18 meq, particularly considering whitening resistance. / G or so.

  In addition, the other physical properties of the component (A) are not particularly limited, but the weight average molecular weight is usually about 3000 to 100,000 from the viewpoint of the initial adhesion, wet heat resistance, whitening resistance, and slipping resistance of the undercoat agent. Preferably, it is about 10000-80000.

  Component (B) is a composition containing a reaction product of triisocyanates (b1) (hereinafter also referred to as (b1) component) and diols (b2) (hereinafter also referred to as (b2) component).

  As the component (b1), triisocyanate as a multimer of various known diisocyanates is preferable. Examples of the diisocyanate include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and lysine diisocyanate, and dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1 , 4-cyclohexane diisocyanate, hydrogenated xylene diisocyanate and hydrogenated tolylene diisocyanate. Examples of multimers include isocyanurate bodies (1,3,5-triazine-2,4,6- (1H, 3H, 5H) trione bodies) and adduct bodies. Among these, an isocyanurate body and / or an adduct body of aromatic diisocyanate are particularly preferable from the viewpoints of heat-and-moisture resistance, whitening resistance and slip-out resistance.

  (B2) As a component, various well-known diol and / or water are mentioned. Specific examples of the diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, neopentyl glycol, 1,6-hexanediol, octanediol, and diene. Examples include propylene glycol, polyethylene glycol, and polypropylene glycol. Among these, particularly from the viewpoint of adhesion to the aluminum thin film, alkylene diols having about 2 to 20 carbon atoms, preferably about 2 to 8 carbon atoms, and particularly about 4 to 8 carbon atoms, and / or water are preferable.

The component (B) can be produced by various known urethanization reactions. The use ratio of the component (b1) and the component (b2) is not particularly limited, but in particular, from the viewpoint of adhesion to the aluminum thin film, the diol of the isocyanate group (NCO ′) and the component (b2) of the component (b1) is usually used. The equivalent ratio [NCO ′ / OH ′] to the hydroxyl group (OH ′) of the class is usually in the range of about 5 to 20, preferably about 10 to 20. On the other hand, when water (H ₂ O) is used as the component (b2), the isocyanate group of the component (b1) reacts with a water molecule, and then undergoes a decarboxylation (CO ₂ ↑) process to form a primary amino group (—NH ₂ ) is generated. Next, this primary amino group reacts with the NCO ′ group of another component (b1). Here, in this series of reaction processes, 2 mol of the isocyanate group of the component (b1) is consumed by 1 mol of water molecules. Therefore, when water (H ₂ O) is used as the component (b2), the equivalent ratio [NCO ′ / OH ′] is calculated on the assumption that it has two hydroxyl groups. In the reaction, if necessary, an organic solvent that does not react with an isocyanate group, for example, the ketone solvent, glycol ether solvent, or ester solvent can be used.

  The component (B) thus obtained has an isocyanate group equivalent of 1 to 10 meq from the viewpoint of compatibility of the undercoat agent of the present invention, pot life, initial adhesion, wet heat and heat resistance, whitening resistance and slipping resistance. / G, preferably about 3 to 6 meq / g.

In the present invention, together with the component (B), if necessary, the diisocyanate,
Triisocyanate other than the component (b1) such as lysine triisocyanate, hexafunctional polyisocyanate (product name “Duranate MHG-80B”, manufactured by Asahi Kasei Chemicals Corporation) and the like can be used.

  The use ratio of the component (A) and the component (B) is not particularly limited. However, considering the compatibility and pot life of the undercoat agent of the present invention, in particular, the whitening resistance and the anti-extraction property, the component (A) The ratio [NCO / OH] of the hydroxyl group equivalent to the isocyanate group equivalent of the component (B) is about 1 to 6, preferably about 2 to 5.

As the component (C), various known epoxy group-containing silicon compounds can be used. Specifically, for example, general formula (1): X—Si (R ¹ ) _a (OR ² ) _3-a (wherein X represents a hydrocarbon group having 1 to 8 carbon atoms including an epoxy group, R ¹ represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, R ² represents a hydrocarbon group having 1 to 8 carbon atoms, and a represents 0 or 1.) Epoxy group-containing alkoxysilane (c1) (Hereinafter also referred to as component (c1)) and / or an epoxy group-containing silsesquioxane (c2) (hereinafter also referred to as component (c2)) obtained by subjecting this to a hydrolysis reaction and a condensation reaction.

  Examples of the component (c1) include glycidoxypropyltrialkoxysilane such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropyltripropoxysilane, and 2 (Epoxycyclohexyl) ethyl such as-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltripropoxysilane A trialkoxysilane etc. are mentioned, These can combine 2 or more types.

  In place of the component (c1), when X in the general formula (1) is, for example, an isocyanate group or a hydrocarbon group such as an alkyl group and a phenyl group, the moisture and heat resistance, The balance between whitening and dropout resistance tends to be poor.

  The component (c2) is silsesquioxane obtained by subjecting the component (c1) to a hydrolysis reaction and a condensation reaction. For the purpose of adjusting the content of the epoxy group, not only the component (c1), but also methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane and phenyltrimethoxysilane. An epoxy group-free alkyltrialkoxysilane such as ethoxysilane (hereinafter also referred to as (c1 ′) component) may be used as a raw material.

  In order to obtain the component (c2), first, the component (c1) and the component (c1 ′) used as necessary are hydrolyzed. Specifically, for example, the component (c1) and the component (c1 ′) used as necessary may be subjected to a hydrolysis reaction in the presence of water and a catalyst. The amount of water is not particularly limited, but [number of moles of water used in hydrolysis reaction] / [total number of moles of alkoxy groups contained in component (c1) and component (c1 ′) used as necessary] ( The molar ratio is usually about 0.4 to 10, preferably about 1. Examples of the catalyst include acidic catalysts (inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, organic acids such as formic acid and acetic acid) and basic catalysts (1,8-diaza-bicyclo [5.4.0] undecene-7. , Organic salts such as 2-ethyl-4-methylimidazole, and inorganic salts such as ammonia and sodium hydroxide), and the amount used is usually the component (c1) and the component (c1 ′) used as necessary The total weight is about 0.1 to 25% by weight, preferably 1 to 10% by weight. The conditions for the hydrolysis reaction are not particularly limited, but usually the reaction temperature is about 0 to 100 ° C, preferably about 20 to 60 ° C, and the reaction time is about 1 minute to 2 hours.

  In the hydrolysis reaction, the organic solvent described above can be used, and the alcohol solvent and glycol ether are particularly preferable.

  By subjecting the obtained hydrolysis reaction product to a condensation reaction, the desired component (c2) can be obtained. The conditions for the condensation reaction are not particularly limited. Usually, the reaction temperature is about 40 to 150 ° C., preferably 60 to 100 ° C., and the reaction time is about 30 minutes to 12 hours. The organic solvent can also be used during the condensation reaction.

  The constant of the component (c2) is not particularly limited. For example, the component [c2] is the number of moles of unreacted hydroxyl groups and alkoxy groups in the component] / [(c1) component and the component (c1 ′) used as necessary. The number of moles of the alkoxy group originally contained] is usually 0.3 or less, the equivalent of the epoxy group is about 100 to 600 g / eq in solid conversion, and the non-volatile content is about 50 to 90% by weight. . In addition, from the obtained component (c2), if necessary, residual alcohol, water, catalyst, solvent and the like may be removed under reduced pressure.

  In place of the component (c2), when X in the general formula (1) is a partial condensate or hydrolyzate of an alkoxy group such as a methoxy group or an ethoxy group, or various known silica particles, The desired effects of the present invention, in particular, the initial adhesiveness, wet heat resistant adhesiveness, whitening resistance, and dropout resistance of the undercoat agent are difficult to balance.

  Although the usage-amount of (C) component is not specifically limited, About 3-20 weight part (solid content conversion) grade is preferable with respect to a total of 100 weight part (solid content conversion) of (A) component and (B) component, Preferably Usually about 5 to 15 parts by weight (in terms of solid content). In such a range, the initial adhesion, wet heat resistance, whitening resistance and drop resistance of the undercoat agent are particularly good.

  The undercoat agent of the present invention is preferably used as a solution of the component (D), and its solid content weight is usually about 5 to 50% by weight. In addition, the undercoat agent of the present invention includes other additives such as urethanization catalysts (tin-based, tertiary amine-based, etc.), Lewis acid catalysts, leveling agents, antioxidants and ultraviolet absorbers, The component (D) can be added as a diluent solvent.

  The plastic with an aluminum thin film of the present invention is a structure having various known plastic substrates (excluding plastic films), a layer made of the undercoat agent according to the present invention, and an aluminum thin film layer.

  Examples of the plastic substrate include polyester (PET, etc.), polyvinyl chloride, polyamide, polyimide, polycarbonate, ABS, polyethylene, and polypropylene. Among these, polyester is preferable in consideration of adhesion with the undercoat layer. The shape of the plastic is not particularly limited, and may be, for example, spherical, columnar, cylindrical, rectangular parallelepiped, or plate-like, and may have irregularities or curved surfaces.

  The plastic film with an aluminum thin film of the present invention is a composite substrate having various known plastic films, a layer comprising the undercoat agent of the present invention, and an aluminum thin film layer.

  Examples of the plastic film include polyester film, polyvinyl chloride film, polyamide film, polyimide film, polycarbonate film, polyethylene film, and polypropylene film. Among these, a polyester film is preferable in consideration of adhesion with the undercoat layer.

  The plastic substrate and the plastic film may be previously provided with functional layers such as a release layer, a hard coat layer, a hard coat layer anchor layer, and a pattern ink layer.

The undercoat layer is formed by applying the undercoat agent of the present invention on the plastic substrate or the plastic film by various known coating means, and usually heating at about 80 to 185 ° C. for about 10 seconds to 5 minutes. It can be obtained by curing. The coating means is not particularly limited, and examples thereof include sprays, roll coaters, reverse roll coaters, gravure coaters, knife coaters, bar coaters, and dot coaters. Moreover, the coating amount of the undercoat agent is not particularly limited, but is usually about 0.01 to 10 g / m ² as a dry solid content.

  The aluminum thin film layer can be obtained by further forming an aluminum seed on the cured undercoat layer by various known thin film forming methods. Examples of the thin film forming method include various physical methods (vacuum thermal vapor deposition, sputtering, etc.) and chemical methods (chemical vapor phase reaction, etc.). The thickness of the aluminum thin film layer is not particularly limited, but is usually about 5 to 500 nm, preferably about 5 to 50 nm.

  Other functional layers may be provided in the plastic with an aluminum thin film and the plastic film with an aluminum thin film of the present invention according to their use. For example, when the film is used for a decorative film for in-mold molding or a decorative film for insert molding, a release layer, a hard coat layer, an anchor layer for a hard coat layer, and a plastic film layer and an undercoat layer A pattern ink layer or the like can be provided. An adhesive layer can also be provided on the aluminum thin film layer.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail through an Example and a comparative example, the scope of the present invention is not limited by these.

  Further, “parts” in the examples represent weight standards. The glass transition temperature is a value measured using a commercially available measuring instrument (product name “DSC8230B”, manufactured by Rigaku Corporation). The hydroxyl group equivalent and the isocyanate group equivalent are calculated values calculated from the number of charged parts of the raw material. The weight average molecular weight is a value measured using a commercially available gel permeation chromatography instrument (product name “HLC-8220GPC”, manufactured by Tosoh Corporation). The micrographs in FIGS. 1 and 2 are taken using a commercially available confocal laser microscope (product name “VK-9500”, manufactured by Keyence Corporation).

<Preparation of component (A)>
Production Example 1
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, 192.0 parts of methyl methacrylate, 7.2 parts of normal butyl acrylate, and 2-hydroxyethyl acrylate 40.8 And 360 parts of methyl ethyl ketone were charged, and the reaction system was set to 80 ° C. Next, 1.2 parts of azobisisobutyronitrile was charged, and the temperature was kept at around 80 ° C. for 5 hours. Next, 2.4 parts of azobisisobutyronitrile was charged, and the reaction system was further kept at the same temperature for 4 hours. Thereafter, by cooling the reaction system to room temperature, a solution (nonvolatile content) of an acrylic copolymer (A-1) having a glass transition temperature of 70 ° C., a hydroxyl group equivalent of 1.42 meq / g (hydroxyl value of 80 mgKOH / g), and a weight average molecular weight of 50,000. 30%).

Production Example 2
A reaction vessel similar to Production Example 1 was charged with 189.6 parts of methyl methacrylate, 4.8 parts of normal butyl acrylate, 45.6 parts of 2-hydroxyethyl methacrylate, and 360.0 parts of methyl ethyl ketone. Was set to 80 ° C. Next, 1.2 parts of azobisisobutyronitrile was charged, and the temperature was kept at around 80 ° C. for 5 hours. Next, 2.4 parts of azobisisobutyronitrile was charged, and the reaction system was further kept at the same temperature for 4 hours. Thereafter, the reaction system was cooled to room temperature, whereby a glass transition temperature of 90 ° C., a hydroxyl group equivalent of 1.42 meq / g (hydroxyl value of 80 mg KOH / g), and a solution (nonvolatile content) of an acrylic copolymer (A-2) having a weight average molecular weight of 50,000. 30%).

Production Example 3
A reaction vessel similar to Production Example 1 was charged with 117.6 parts of methyl methacrylate, 81.6 parts of normal butyl acrylate, 40.8 parts of 2-hydroxyethyl acrylate, and 360.0 parts of methyl ethyl ketone. Was set to 80 ° C. Next, 1.2 parts of azobisisobutyronitrile was charged, and the temperature was kept at around 80 ° C. for 5 hours. Next, 2.4 parts of azobisisobutyronitrile was charged, and the reaction system was further kept at the same temperature for 4 hours. Thereafter, the reaction system was cooled to room temperature, whereby a solution (nonvolatile content) of an acrylic copolymer (A-3) having a glass transition temperature of 10 ° C., a hydroxyl group equivalent of 1.42 meq / g (hydroxyl value of 80 mgKOH / g), and a weight average molecular weight of 55,000. 30%).

Production Example 4
In a reaction vessel similar to Production Example 1, 194.4 parts of methyl methacrylate, 14.4 parts of normal butyl acrylate, 31.2 parts of 2-hydroxyethyl acrylate, and 360.0 parts of methyl ethyl ketone were charged. Was set to 80 ° C. Next, 1.2 parts of azobisisobutyronitrile was charged, and the temperature was kept at around 80 ° C. for 5 hours. Next, 2.4 parts of azobisisobutyronitrile was charged, and the reaction system was further kept at the same temperature for 4 hours. Thereafter, the reaction system was cooled to room temperature, whereby a glass transition temperature of 70 ° C., a hydroxyl equivalent of 1.07 meq / g (hydroxyl value of 60 mg KOH / g), and a solution (nonvolatile content) of an acrylic copolymer (A-4) having a weight average molecular weight of 50000 30%).

Production Example 5
In a reaction vessel similar to Production Example 1, 201.6 parts of methyl methacrylate, 4.8 parts of normal butyl acrylate, 33.6 parts of 2-hydroxyethyl methacrylate, and 360.0 parts of methyl ethyl ketone were charged. Was set to 80 ° C. Next, 1.2 parts of azobisisobutyronitrile was charged, and the temperature was kept at around 80 ° C. for 5 hours. Next, 2.4 parts of azobisisobutyronitrile was charged, and the reaction system was further kept at the same temperature for 4 hours. Thereafter, the reaction system was cooled to room temperature, whereby a solution (nonvolatile content) of an acrylic copolymer (A-5) having a glass transition temperature of 90 ° C., a hydroxyl group equivalent of 1.07 meq / g (hydroxyl value of 60 mgKOH / g), and a weight average molecular weight of 52,000. 30%).

Production Example 6
In the same reaction vessel as in Production Example 1, 70.8 parts of methyl methacrylate, 84.0 parts of normal butyl acrylate, 64.8 parts of 2-hydroxyethyl acrylate, 20.4 parts of styrene, and 360.0 methyl ethyl ketone The reaction system was set to 80 ° C. Next, 1.2 parts of azobisisobutyronitrile was charged, and the temperature was kept at around 80 ° C. for 5 hours. Next, 2.4 parts of azobisisobutyronitrile was charged, and the reaction system was further kept at the same temperature for 4 hours. Thereafter, the reaction system was cooled to room temperature, whereby a solution (nonvolatile content) of an acrylic copolymer (A-6) having a glass transition temperature of 0 ° C., a hydroxyl group equivalent of 2.31 meq / g (hydroxyl value of 130 mgKOH / g), and a weight average molecular weight of 55,000. 30%).

Production Example 7
A reaction vessel similar to Production Example 1 was charged with 148.8 parts of methyl methacrylate, 60.0 parts of normal butyl acrylate, 31.2 parts of 2-hydroxyethyl acrylate, and 360.0 parts of methyl ethyl ketone. Was set to 80 ° C. Next, 1.2 parts of azobisisobutyronitrile was charged, and the temperature was kept at around 80 ° C. for 5 hours. Next, 2.4 parts of azobisisobutyronitrile was charged, and the reaction system was further kept at the same temperature for 4 hours. Thereafter, by cooling the reaction system to room temperature, a solution (nonvolatile content) of an acrylic copolymer (A-7) having a glass transition temperature of 30 ° C., a hydroxyl group equivalent of 1.07 meq / g (hydroxyl value of 60 mgKOH / g), and a weight average molecular weight of 50,000. 30%).

Production Example 8
In the same reaction vessel as in Production Example 1, 166.8 parts of methyl methacrylate, 8.4 parts of normal butyl acrylate, 24.0 parts of stearyl acrylate, 40.8 parts of 2-hydroxyethyl acrylate, and 360. 0 parts was charged and the reaction system was set to 80 ° C. Next, 1.2 parts of azobisisobutyronitrile was charged, and the temperature was kept at around 80 ° C. for 5 hours. Next, 2.4 parts of azobisisobutyronitrile was charged, and the reaction system was further kept at the same temperature for 4 hours. Thereafter, the reaction system was cooled to room temperature, whereby a solution (nonvolatile content) of an acrylic copolymer (A-8) having a glass transition temperature of 60 ° C., a hydroxyl group equivalent of 1.42 meq / g (hydroxyl value of 80 mg KOH / g), and a weight average molecular weight of 53,000. 30%).

Production Example 9
In a reaction vessel similar to Production Example 1, 184.8 parts of methyl methacrylate, 7.2 parts of normal butyl acrylate, 40.8 parts of 2-hydroxyethyl acrylate, 7.2 parts of acrylic acid, and 360.0 methyl ethyl ketone The reaction system was set to 80 ° C. Next, 1.2 parts of azobisisobutyronitrile was charged, and the temperature was kept at around 80 ° C. for 5 hours. Next, 2.4 parts of azobisisobutyronitrile was charged, and the reaction system was further kept at the same temperature for 4 hours. Thereafter, the reaction system was cooled to room temperature, whereby a glass transition temperature of 70 ° C., a hydroxyl group equivalent of 1.42 meq / g (hydroxyl value 80 mgKOH / g), a carboxyl group equivalent of 0.41 meq / g (acid value 23 mgKOH / g) and a weight average. A solution (non-volatile content 30%) of an acrylic copolymer (A-9) having a molecular weight of 54,000 was obtained.

Production Example 10
In a reaction vessel similar to Production Example 1, 184.8 parts methyl methacrylate, 7.2 parts normal butyl acrylate, 40.8 parts 2-hydroxyethyl acrylate, 7.2 parts methacrylic acid, and 360.0 methyl ethyl ketone The reaction system was set to 80 ° C. Next, 1.2 parts of azobisisobutyronitrile was charged, and the temperature was kept at around 80 ° C. for 5 hours. Next, 2.4 parts of azobisisobutyronitrile was charged, and the reaction system was further kept at the same temperature for 4 hours. Thereafter, by cooling the reaction system to room temperature, glass transition temperature 70 ° C., hydroxyl group equivalent 1.42 meq / g (hydroxyl value 80 mgKOH / g), carboxyl group equivalent 0.34 meq / g (acid value 19 mgKOH / g) and weight average. A solution (non-volatile content 30%) of an acrylic copolymer (A-10) having a molecular weight of 55000 was obtained.

Comparative production example 1
In the same reaction vessel as in Production Example 1, 177.6 parts of methyl methacrylate, 20.9 parts of normal butyl acrylate, 17.5 parts of 2-hydroxyethyl acrylate, 24.0 parts of styrene, and 360.0 methyl ethyl ketone The reaction system was set to 80 ° C. Next, 1.2 parts of azobisisobutyronitrile was charged, and the temperature was kept at around 80 ° C. for 5 hours. Next, 2.4 parts of azobisisobutyronitrile was charged, and the reaction system was further kept at the same temperature for 4 hours. Thereafter, the reaction system was cooled to room temperature, whereby a glass transition temperature of 70 ° C., a hydroxyl equivalent of 0.62 meq / g (hydroxyl value of 35 mgKOH / g), and a solution of acrylic copolymer (A) having a weight average molecular weight of 45000 (nonvolatile content: 30% )

Comparative production example 2
A reaction vessel similar to Production Example 1 was charged with 123.6 parts of methyl methacrylate, 16.8 parts of normal butyl acrylate, 99.6 parts of 2-hydroxyethyl acrylate, and 360.0 parts of methyl ethyl ketone. Was set to 80 ° C. Next, 1.2 parts of azobisisobutyronitrile was charged, and the temperature was kept at around 80 ° C. for 5 hours. Next, 2.4 parts of azobisisobutyronitrile was charged, and the reaction system was further kept at the same temperature for 4 hours. Thereafter, the reaction system was cooled to room temperature, whereby a solution of an acrylic copolymer (b) having a glass transition temperature of 30 ° C., a hydroxyl group equivalent of 3.56 meq / g (hydroxyl value of 200 mgKOH / g), and a weight average molecular weight of 48,000 (nonvolatile content: 30% )

MMA: methyl methacrylate nBA: n-butyl acrylate SMA: stearyl acrylate HEA: 2-hydroxyethyl acrylate HEMA: 2-hydroxyethyl methacrylate AA: acrylic acid MAA: methacrylic acid St: styrene

<Preparation of component (B)>
Production Example 11
In a reaction vessel similar to Production Example 1, 445.5 parts of isocyanurate of tolylene diisocyanate (product name “Coronate 2030”, isocyanate group equivalent 3.8 meq / g) and 5.0 of 1,6-hexanediol were added. And 308.6 parts of methyl ethyl ketone were charged, and urethanization reaction was carried out at 60 ° C. for 3 hours. Thereafter, by cooling to room temperature, an isocyanate composition (B-1) (isocyanate group equivalent: 3.3 meq / g) was obtained.

Production Example 12
The same reaction vessel as in Production Example 1 was charged with 445.5 parts of Coronate 2030, 0.75 parts of water, 273.5 parts of methyl ethyl ketone, and 25.2 parts of propylene glycol monomethyl ether acetate at 60 ° C. for 3 hours. Urethane reaction was carried out. Thereafter, by cooling to room temperature, an isocyanate composition (B-2) (isocyanate group equivalent: 3.3 meq / g) was obtained.

<Preparation of component (c2)>
In a reaction vessel similar to Production Example 1, 300 g of 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name “KBM-403”) as component (c1), 71.8 g of ion-exchanged water ( [Mole number of water used in hydrolysis reaction] / [Total number of moles of alkoxy groups contained in 3-glycidoxypropyltrimethoxysilane] (molar ratio) = 1.05), 1.5 g of 95% formic acid, toluene 100 g was charged and hydrolyzed at room temperature for 30 minutes. In the hydrolysis reaction, [number of moles of hydroxyl group generated by hydrolyzing 3-glycidoxypropyltrimethoxysilane] / [number of moles of alkoxy group originally contained in 3-glycidoxypropyltrimethoxysilane] ] (Molar ratio) was 0.9. After the hydrolysis reaction, when the temperature of the reaction system was raised to 70 ° C., methanol generated by the hydrolysis began to be distilled out of the system. The temperature was raised to 75 ° C. over 30 minutes, and water generated by the condensation reaction was distilled off. After further reacting at 75 ° C. for 30 minutes, 100 g of diethylene glycol dimethyl ether was added, and the pressure was reduced stepwise at 50 ° C. for 3 hours to distill off the remaining methanol, water, formic acid, and toluene. Diethylene glycol dimethyl ether was further added so that the solid content concentration was 15%, to obtain 1500 g of an epoxy group-containing silsesquioxane (c2) (hereinafter also referred to as component (c2)). The epoxy equivalent of (c2) was 1200 g / eq (180 g / eq in solid conversion).

<Preparation of undercoat agent>
Example 1
(A-1) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), (c1) Epoxy group-containing alkoxysilane (trade name “KBM-403”, 0.56 parts (manufactured by Shin-Etsu Chemical Co., Ltd.) and 10.6 parts of methyl ethyl ketone were mixed well to prepare an undercoat agent.

Example 2
(A-2) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), KBM-403 0.56 parts, and methyl ethyl ketone 10.6 parts are mixed well. An undercoat agent was prepared.

Example 3
(A-3) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), KBM-403 0.56 parts, and methyl ethyl ketone 10.6 parts are mixed well. An undercoat agent was prepared.

Example 4
(A-4) Component 10.0 parts, (B-1) Component 6.5 parts (NCO / OH = 2.0), KBM-403 0.5 part, and methyl ethyl ketone 10.2 parts are mixed well. An undercoat agent was prepared.

Example 5
(A-5) Component 10.0 parts, (B-1) Component 6.5 parts (NCO / OH = 2.0), KBM-403 0.5 part, and methyl ethyl ketone 10.2 parts are mixed well. An undercoat agent was prepared.

Example 6
(A-6) Component 10.0 parts, (B-1) Component 14.0 parts (NCO / OH = 2.0), KBM-403 0.72 parts, and methyl ethyl ketone 14.8 parts are mixed well. An undercoat agent was prepared.

Example 7
(A-7) Component 10.0 parts, (B-1) Component 6.5 parts (NCO / OH = 2.0), KBM-403 0.5 part, and methyl ethyl ketone 10.2 parts are mixed well. An undercoat agent was prepared.

Example 8
(A-8) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), KBM-403 0.56 part, and methyl ethyl ketone 10.6 parts are mixed well. An undercoat agent was prepared.

Example 9
(A-9) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), KBM-403 0.56 parts, and methyl ethyl ketone 10.6 parts are mixed well. An undercoat agent was prepared.

Example 10
(A-10) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), KBM-403 0.56 parts, and methyl ethyl ketone 10.6 parts are mixed well. An undercoat agent was prepared.

Example 11
10. (A-1) component 10.0 parts, (B-1) component 8.6 parts (NCO / OH = 2.0), (c2) component 0.7 part obtained in the said preparation example, and methyl ethyl ketone 11. Four parts were mixed well to prepare an undercoat agent.

Example 12
(A-1) component 10.0 parts, (B-1) component 8.6 parts (NCO / OH = 2.0), (c2) component 0.35 parts obtained in the above preparation example, and methyl ethyl ketone 10. 7 parts were mixed well to prepare an undercoat agent.

Example 13
(A-1) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), KBM-403 0.28 parts, and methyl ethyl ketone 10.4 parts are mixed well. An undercoat agent was prepared.

Example 14
(A-1) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), KBM-403 0.84 part, and methyl ethyl ketone 12.6 parts were mixed well. An undercoat agent was prepared.

Example 15
(A-1) Component 10.0 parts, (B-1) Component 4.3 parts (NCO / OH = 1.0), KBM-403 0.21 part, and methyl ethyl ketone 8.3 parts are mixed well. An undercoat agent was prepared.

Example 16
(A-1) Component 10.0 parts, (B-1) Component 12.8 parts (NCO / OH = 3.0), KBM-403 0.34 parts, and methyl ethyl ketone 12.7 parts were mixed well. An undercoat agent was prepared.

Example 17
(A-1) Component 10.0 parts, (B-2) Component 6.5 parts (NCO / OH = 2.0), KBM-403 0.5 part, and methyl ethyl ketone 10.6 parts are mixed well. An undercoat agent was prepared.

Comparative Example 1
(A) Component 10.0 parts, (B-1) Component 3.8 parts (NCO / OH = 2.0), KBM-403 0.42 part, and methyl ethyl ketone 8.6 parts are mixed well, and undercoat An agent was prepared.

Comparative Example 2
(B) Component 10.0 parts, (B-1) Component 10.7 parts (NCO / OH = 2.0), KBM-403 0.63 parts, and methyl ethyl ketone 12.8 parts are mixed well, and undercoat An agent was prepared.

Comparative Example 3
(A-1) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), (c1) Instead of component 3-isocyanatopropyltriethoxysilane (trade name “KBE”) -9007 "(Shin-Etsu Chemical Co., Ltd.) 0.56 part and 11.5 parts of methyl ethyl ketone were mixed well to prepare an undercoat agent.

Comparative Example 4
(A-1) component 10.0 parts, (B-1) component 8.6 parts (NCO / OH = 2.0), (c1) instead of component tris- (trimethoxysilylpropyl) isocyanurate The name “KBM-9659” manufactured by Shin-Etsu Chemical Co., Ltd.) 0.56 part and 11.5 parts of methyl ethyl ketone were mixed well to prepare an undercoat agent.

Comparative Example 5
(A-1) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), (c1) In place of component, decyltrimethoxysilane (trade name “KBM-3103” 0.56 parts (manufactured by Shin-Etsu Chemical Co., Ltd.) and 11.5 parts of methyl ethyl ketone were mixed well to prepare an undercoat agent.

Comparative Example 6
(A-1) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), (c1) Instead of component phenyltrimethoxysilane (trade name “KBM-103” 0.56 parts (manufactured by Shin-Etsu Chemical Co., Ltd.) and 11.5 parts of methyl ethyl ketone were mixed well to prepare an undercoat agent.

Comparative Example 7
(A-1) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), (c1) In place of component, methyltrimethoxysilane (trade name “KBM-13”) 0.56 parts (manufactured by Shin-Etsu Chemical Co., Ltd.) and 11.5 parts of methyl ethyl ketone were mixed well to prepare an undercoat agent.

Comparative Example 8
(A-1) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), (c1) Instead of component, methyl silicate oligomer (trade name “MKC silicate MS-51 “Mitsubishi Chemical Co., Ltd.) 0.56 part and methyl ethyl ketone 11.5 parts were mixed well to prepare an undercoat agent.

Comparative Example 9
(A-1) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), (c2) In place of component, organosilica sol (trade name “MEK-ST” NISSAN CHEMICAL 1.86 parts of Kogyo Co., Ltd. and 10.2 parts of methyl ethyl ketone were mixed well to prepare an undercoat agent.

Comparative Example 10
(A-1) 10.0 parts of component, 7.5 parts of coronate 2030 (NCO / OH = 2.0), 0.68 parts of KBM-403, and 10.6 parts of methyl ethyl ketone are mixed well, and an undercoat agent is added. Prepared.

<Preparation of test panel>
After drying and curing a commercially available hard coating agent (trade name “Aronix M305”, a mixture of pentaerythritol tri and tetraacrylate, manufactured by Toa Gosei Co., Ltd.) on a polyethylene terephthalate film that has been subjected to mold release treatment The film was coated so that the film thickness was 5 μm, and the curing treatment was performed at an illuminance of 100 mj / cm ² . Next, the undercoat agent according to Example 1 was applied onto the hard coat layer with a bar coater so that the dry film thickness was 1 μm.

  Next, the obtained coated film was cured by a normal air dryer (150 ° C., 60 seconds). Next, a commercially available vapor deposition apparatus (product name “NS-1875-Z”, manufactured by Nishiyama Seisakusho Co., Ltd.) was used for the coating film to obtain an aluminum vapor deposition film having a vapor deposition layer thickness of 50 nm.

  Next, a vinyl chloride-vinyl acetate copolymer adhesive (trade name “Kanevirak L-CM” manufactured by Kaneka Co., Ltd.) is applied on the aluminum vapor-deposited layer with a bar coater so that the dry film thickness becomes 1 μm. Worked. Next, the obtained coated film was dried with a normal air dryer (80 ° C., 10 seconds). This was thermally transferred to a commercially available acrylic plate and used as a test panel of Example 1. Test panels were similarly prepared for the undercoat agents of other examples and comparative examples.

(Initial adhesion)
For each test panel, put 100 square grids on the hard coat surface with a cutter knife, affix an adhesive tape (product name “Serotape (registered trademark)”, manufactured by Nichiban Co., Ltd.), and peel it off in a vertical direction. However, the aluminum surface did not peel off. (Indicated in each table as 5)

(Moisture and heat adhesion)
The adhesion after each test panel was placed under constant temperature and humidity conditions of 65 ° C. and 95% × 24 hours was evaluated according to the following criteria according to the same method as the above initial adhesion.

5 ... No peeling is observed 4 ... Less than 5% peeling is observed on the aluminum surface.
3: Peeling of 5% or more and less than 20% is observed on the aluminum surface.
2: Peeling of 20% to less than 50% is observed on the aluminum surface.
1 ... 50% to 100% peeling is observed on the aluminum surface.

(Whitening resistance)
The whitening state after each test panel was placed under constant temperature and humidity conditions of 65 ° C. and 95% × 24 hours was visually evaluated according to the following criteria.
5 ... No whitening occurs on the aluminum surface, and the metallic luster is maintained.
4 ... Slight whitening occurs on the aluminum surface, but the metallic luster is almost maintained.
3 ... Slight whitening occurs on the entire aluminum surface, and a slight loss of metallic luster is observed.
2 ... The whitening of the entire aluminum surface is strongly generated, and the loss of metallic luster is observed.
1 ... Whitening occurs more strongly on the entire aluminum surface, and the metallic luster is completely lost.

(Omission resistance)
Each test panel was visually evaluated according to the following criteria for the state of the aluminum layer coming off after being placed under constant temperature and humidity conditions of 65 ° C. and 95% × 24 hours.

5 ... There are no gaps on the aluminum surface.
4 ... Slight detachment has occurred partially on the aluminum surface.
3 ... Slight detachment occurs on the entire aluminum surface.
2 ... Many omissions occur on the entire aluminum surface.
1 ... Many large omissions occur on the entire aluminum surface.

Claims (11)

A reaction product of a hydroxy group-free alkyl (meth) acrylate (a1) and a hydroxy group-containing alkyl (meth) acrylate (a2), having a glass transition temperature of 0 to 100 ° C. and a hydroxyl group equivalent of 0.00. An acrylic copolymer (A) that is 8-3.5 meq / g;
An isocyanate composition (B) containing a reaction product of triisocyanates (b1) and diols and / or water (b2) and having an isocyanate group equivalent of 1 to 10 meq / g;
Formula _{^{(1): X-Si (}} R 1) a (OR 2) 3-a ( wherein, X is a hydrocarbon group having 1 to 8 carbon atoms containing an epoxy group, ^{R 1} is hydrogen or a carbon atoms An epoxy group-containing alkoxysilane (c1) represented by ˜8 hydrocarbon group, R ² is a hydrocarbon group having 1 to 8 carbon atoms, and a is 0 or 1. An epoxy group-containing silicon compound (C) comprising an epoxy group-containing silsesquioxane (c2) obtained by reaction and condensation reaction;
An undercoat agent for plastics with an aluminum thin film, containing The undercoat agent of Claim 1 whose carbon number of the alkyl group of (a1) component is 1-20. The undercoat agent according to claim 1 or 2, wherein the hydroxyalkyl group of the component (a2) has 1 to 4 carbon atoms. The undercoat agent according to any one of claims 1 to 3, wherein the component (b1) is an aromatic diisocyanate trimer and the component (b2) is an alkylene diol having 2 to 8 carbon atoms. The undercoat agent according to any one of claims 1 to 4, wherein a ratio [NCO / OH] of the hydroxyl group equivalent of the component (A) and the isocyanate group equivalent of the component (B) is 1 to 6. The undercoat agent according to any one of claims 1 to 5, wherein the amount of component (C) used is 3 to 20 parts by weight relative to 100 parts by weight of the sum of component (A) and component (B). The undercoat agent according to any one of claims 1 to 6, which is used as a solution of an organic solvent (D). A plastic with an aluminum thin film, comprising a plastic substrate (excluding a plastic film), a layer comprising the undercoat agent according to any one of claims 1 to 7, and an aluminum thin film layer. The plastic film with an aluminum thin film which has a plastic film, the layer which consists of an undercoat agent in any one of Claims 1-7, and an aluminum thin film layer. A decorative film for in-mold molding, comprising the plastic film with an aluminum thin film according to claim 9 as a member. A decorative film for insert molding, comprising the plastic film with an aluminum thin film according to claim 9 as a member.