TW201627430A - Undercoating agent for plastic with aluminum thin film, plastic with aluminum thin film, plastic film with aluminum thin film, decoration film for in-mold molding, and decoration film for insert molding - Google Patents

Abstract

To provide a novel undercoating agent by which the binding property of an aluminum thin film and a plastic base material will not degenerate even when the plastic attached with the aluminum thin film is placed under high temperature and high humidity. In addition, no whitening part or transparent spots will be generated on the aluminum thin film surface. As the undercoating agent, this invention uses a composition which comprises: a specific acrylic acid-based copolymer (A) with a glass transition temperature of 0 to 100 DEG C and a hydroxyl equivalent of 0.8 to 3.5 meq/g; an isocyanate ester composition (B) comprising a reactant of triisocyanate ester (b1) and diol and/or water (b2) and having an isocyanate group equivalent of 1 to 10 meq/g; and a silicon compound containing epoxy group (C) composed of alkoxy silane having epoxy group (c1) and/or a semi-siloxane having epoxy group (c2), wherein the semi-siloxane having epoxy group (c2) is obtained by subjecting the alkoxy silane having epoxy group (c1) to hydrolysis and condensation reactions.

Description

Plastic primer with aluminum film, plastic with aluminum film and aluminum Plastic film for film, decorative film for in-mold forming, and decorative film for insert molding

The present invention relates to a primer, a plastic film with an aluminum film obtained by using the primer, a plastic film with an aluminum film, and a decorative film for in-mold forming and insert molding using the plastic film as a member, The primer is used to bond the aluminum film to the plastic substrate.

A plastic with an aluminum film means that a film made of aluminum is formed on the surface of the plastic substrate. In particular, a plastic film with an aluminum film having an aluminum film thickness of about several tens of nanometers in a surface area of a plastic film is appreciated and used as a member for in-mold forming or insert molding, and can impart a metal to a molded article. Since it has a design such as a feeling or a mirror, it has been provided in recent years for housings of various electronic products such as mobile phones or audio products, personal computers, and automobile interior parts.

Further, in order to bond an aluminum film to a plastic substrate, a primer having various polymers as a main component is often used.

For example, Patent Document 1 describes a primer comprising a polyol and a polyisocyanate having a specific glass transition temperature and When the hydroxyl group is used, the adhesion between the plastic film and the aluminum film can be improved by the primer.

Further, Patent Document 2 describes a primer comprising a specific hydroxyl group-containing acrylic copolymer and a polyisocyanate, the acrylic copolymer being composed of a specific alkyl (meth)acrylate and a hydroxyl group-containing (methyl group). ) composed of acrylate. Further, by the primer, not only the adhesion between the plastic film and the vapor-deposited aluminum film is good, but even if the plastic film with the aluminum film is placed at a high temperature, the aluminum film can be prevented from being whitened ( Whitening).

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Laid-Open Patent Publication No. 2009-227837

Patent Document 2: Japanese Laid-Open Patent Publication No. 2011-132521

However, if the aluminum film-attached plastic obtained by using the primer of Patent Document 1 is placed in a high temperature and high humidity state, there is a problem that the adhesion between the plastic substrate and the aluminum film is lowered, or in the aluminum film. The whitening part is produced.

Further, if the plastic film with the aluminum film of Patent Document 2 is placed in a high temperature and high humidity state, the following problem is found: as shown in Fig. 2, aluminum The film produces a large number of minute transparent portions (hereinafter also referred to as "clear spots").

The problem of the present invention is to provide a novel primer which does not reduce the adhesion of the aluminum film to the plastic substrate even under high temperature and high humidity, and does not produce whitened portions or transparent spots on the aluminum film.

The inventors believe that the aforementioned "clear speckle" is formed by a certain reaction of aluminum and water, and is transparent in the visible light region, and therefore, as shown in Fig. 2, it looks like on the aluminum film. Produces numerous tiny holes.

Further, studies have been made to solve the problem of transparent spots and maintain the adhesion and whitening resistance, and as a result, it has been found that a specific epoxy group-containing decane compound is further added to a primer containing a specific acrylic polyol and a polyisocyanate. Thereby, a primer which can solve the aforementioned problems can be obtained.

That is, the present invention relates to a primer for plastics with an aluminum film, comprising: an acrylic copolymer (A) which is a hydroxyl group-free (meth)acrylic acid alkyl ester (a1) and a hydroxyl group-containing a reactant of the alkyl (meth)acrylate (a2) 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 triisocyanate (b1) a reactant with a diol and/or water (b2), and an isocyanate equivalent of 1 to 10 meq/g; and an epoxy group-containing oxime compound (C) derived from an epoxy group-containing alkoxy group The base alkane (c1) and/or the epoxy group-containing semi-oxane (c2), the epoxy group-containing alkoxydecane (c1) is represented by the formula (1), that is, X-Si (R) ¹ ) _a (OR ² ) _3-a (in the formula (1), X represents a hydrocarbon group having an epoxy group having 1 to 8 carbon atoms, R ¹ represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, and R ² represents a hydrocarbon group having 1 to 8 carbon atoms, a represents 0 or 1), and the epoxy group-containing semi-oxane (c2) is a hydrolysis reaction and a condensation reaction of the epoxy group-containing alkoxydecane (c1) Made.

Further, the present invention relates to a plastic coated with an aluminum film having a plastic substrate (excluding a plastic film), a layer composed of the primer, and an aluminum film layer.

Further, the present invention relates to a plastic film with an aluminum film, which has a plastic film, a layer composed of the primer, and an aluminum film layer.

Further, the present invention relates to a decorative film for in-mold forming and a decorative film for insert molding, which are made of the above-mentioned plastic film with an aluminum film.

The primer of the present invention is a transparent composition and has a long service life at room temperature. When the primer is used, the initial adhesion between the aluminum film and the plastic substrate (hereinafter also referred to as initial adhesion), and the adhesion between the aluminum film under high temperature and high humidity and the plastic substrate can be obtained (hereinafter It is also known as heat-resistant and heat-resistant adhesiveness, and the whitening resistance and the transparent speckle resistance of the aluminum film surface (hereinafter, simply referred to as whitening resistance and transparent speckle resistance).

The aluminum film-attached plastic (excluding the film-shaped plastic) of the present invention has good initial adhesion, wet heat resistance, whitening resistance, and transparent speckle resistance. The plastic with aluminum film can be provided, for example, for bottles and cans It can also be used for housings of various electronic products such as covers, mobile phones or audio products, personal computers, and automotive interior parts.

Similarly, the aluminum film-attached plastic film of the present invention has good initial adhesion, wet heat resistance, whitening resistance, and transparent speckle resistance. The plastic film with an aluminum film is suitable for, for example, a member for in-mold forming or inserting a decorative film for molding, and is suitable as a packaging material such as a gas barrier film, or a transparent conductive sheet or a film capacitor (film). Capacitor), the component of the label.

Fig. 1 is a micrograph (400 times) of the vapor-deposited surface of the vapor-deposited aluminum PET film of Example 1, which was extremely smooth, and it was found that no transparent spots were formed.

Fig. 2 is a micrograph (400 times) of the vapor-deposited surface of the vapor-deposited aluminum PET film of Comparative Example 1, and it was found that transparent spots were formed on the vapor deposition surface.

The primer of the present invention is a composition which is a specific acrylic copolymer (A) (hereinafter also referred to as (A) component) and an isocyanate composition (B) (hereinafter also referred to as (B) The component () and the epoxy group-containing hydrazine compound (C) (hereinafter also referred to as component (C)) are essential components.

The component (A) is a copolymer which is a hydroxyl group-free (meth)acrylic acid alkyl ester (a1) (hereinafter also referred to as (a1) component) and a hydroxyl group-containing (meth)acrylic acid alkyl ester ( A2) (hereinafter also referred to as component (a2)) is reacted.

The (a1) component is not particularly limited as long as it is an alkyl (meth)acrylate having no hydroxyl group in the molecule, and various known alkyl (meth)acrylates can be used. Specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and dibutyl (meth)acrylate. Ester, tert-butyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cetyl (meth)acrylate, dodecane (meth)acrylate Ester, octadecyl (meth)acrylate, eicosanyl (meth)acrylate, behenyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate And (meth)acrylic acid cyclopentyl ester, and isobornyl (meth)acrylate, etc., These compounds may be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of particularly contributing to the improvement of the transparent speckle resistance of the primer of the present invention, an alkyl (meth)acrylate having an alkyl group having a carbon number of about 1 to 20 is preferred. Further, by combining the components (a1) having different carbon numbers of the alkyl groups, physical properties such as glass transition temperature of the component (A) can be adjusted.

The component (a2) is a monomer which must be used, and is not particularly limited as long as it is a (meth)acrylic acid alkyl ester having a hydroxyl group in the molecule, and various known alkyl (meth)acrylates can be used, and the component (a2) can be used. The object is to impart a hydroxyl group to the component (A) and react it with the component (B) and the component (C). Specific examples thereof include hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. 3-hydroxybutyl acrylate, 4-hydroxybutyl (meth) acrylate, hydroxycyclohexyl (meth) acrylate, 4-(hydroxymethyl)cyclohexylmethyl (meth) acrylate, and 2- 4-(hydroxymethyl)cyclohexylmethyl hydroxypropionate And these compounds may be used alone or in combination of two or more. In particular, from the viewpoint of the lifespan of the primer of the present invention, etc., the alkyl (meth)acrylate having a hydroxyalkyl group having a carbon number of about 1 to 4 is preferred.

Furthermore, in the present invention, as a constituent monomer of the component (A), a monomer which does not conform to any of the components (a1) and (a2) (hereinafter also referred to as (a3) component) may be used in combination. . Specific examples thereof include (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, 3-carboxypropyl (meth)acrylate, 4-carboxybutyl (meth)acrylate, and 3-butyl α,β unsaturated carboxylic acids such as enoic acid, 4-pentenoic acid, 5-hexenoic acid, maleic acid, crotonic acid, maleic anhydride, fumaric acid, and itaconic acid; styrene, α-methyl Styrene such as styrene and tributyl styrene; 2,4,4-trimethyl-1-pentene, 3-methyl-1-butene, 3-methyl 1-pentene, 1 -alphaolefins such as hexene, vinylcyclohexane, and 2-methylvinylcyclohexane; (meth)allyl alcohol, 4-penten-1-ol, 1-methyl-3-butene Unsaturated alcohols such as 1-propanol and 5-hexen-1-ol; phenyl (meth)acrylate, benzyl (meth)acrylate, and 4-methylbenzyl (meth)acrylate (A) Acryl acrylate; dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylate Dialkylaminoalkyl (meth)acrylate such as dimethylaminopropyl propyl ester or diethylaminopropyl (meth)acrylate, and dimethylaminoethyl (meth) propylene hydride , dialkylamine such as diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide and diethylaminopropyl (meth) acrylamide Alkyl (meth) acrylamide and its salts; N, N-dimethyl (meth) acrylamide, diacetone (meth) acrylamide, isopropyl (meth) acrylamide, a chain transfer monomer such as 2-(methyl)acrylamido-2-methylpropanesulfonic acid, 2-(methyl)acrylamido-2-methylpropionic acid or a salt thereof; vinylamine, Other monofunctional monomers such as aminoethyl methacrylate, allyl mercaptan, and glycidyl (meth) acrylate; methylene bis(methyl) acrylamide, exoethyl bis (methyl) Bis(meth) acrylamide such as acrylamide and hexamethylene bis(meth) acrylamide; ethylene glycol di(meth) acrylate and diethylene glycol di(meth) acrylate Di(meth)acrylate; divinyl ester of divinyl adipate and divinyl sebacate; diallyldimethylammonium, diallyl phthalate, chlorinated diene Diallyl chlorendate, and difunctional monomers such as divinylbenzene; 1,3,5-tripropenyl hexahydro-s- three , triallyl isocyanurate, triallylamine, triallyl trimellitate, and trifunctional monomer such as N,N-diallylpropenylamine; tetramethylolethane Tetraacrylate, tetraallyl pyromellitate, and tetrafunctional monomers such as N,N,N',N'-tetraallyl-1,4-diaminobutane; acrylonitrile and methyl Acrylonitrile such as acrylonitrile; acrylamide such as acrylamide, methacrylamide, N-methylol acrylamide, and N-methylol methacrylamide.

When the (a1) component and the (a2) component are used as the constituent monomers of the component (A), the use ratio of these components is not particularly limited, and is generally as follows.

(a1) Ingredients: generally about 45 to 97 mol%, preferably about 65 to 90 mol%

(a2) Ingredients: generally about 3 to 45 mol%, preferably about 10 to 35 mol%

Further, when the component (a3) is used in combination with the component (a1) and the component (a2), the ratio of use of these components is not particularly limited, and is generally as follows.

(a1) Ingredients: generally about 65 to 90 mol%, preferably about 70 to 85 mol%

(a2) Ingredients: generally about 5 to 35 mol%, preferably about 10 to 30 mol%

(a3) Ingredients: generally about 1 to 20 mol%, preferably about 1 to 15 mol%

The component (A) can be produced by various known methods. Specifically, for example, in the absence of a solvent or in an organic solvent (D) (hereinafter also referred to as a component (D)), it is generally in the presence of a radical polymerization initiator at a temperature of about 80 to 180 ° C. The (a1) component and the component (a2) and the component (a3) used as needed may be copolymerized for about 1 to 10 hours.

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; methanol, ethanol, and n-propanol; a low molecular alcohol solvent such as isopropyl alcohol or butanol; ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, a glycol ether solvent such as diethylene glycol diethyl ether or propylene glycol monomethyl ether acetate; an ester solvent such as ethyl acetate, butyl acetate, acesulfame acetate, and ceramide acetate; Solvesso# 100 and Solvesso #150 (both trade names, manufactured by ExxonMobil) and other petroleum solvents; other chloroform and dimethylformamide The amount of the component (D) to be used is such that the solid content of the solution containing the component (A) is in the range of about 10 to 50% by weight.

Examples of the radical polymerization initiator include hydrogen peroxide, ammonium persulfate, potassium persulfate, butyl peroxybenzoate, dicumyl peroxide, lauryl peroxide, and 2, 2'. - azobisisobutyronitrile, and dimethyl 2,2'-azobisisobutyrate; the radical polymerization initiator is used in an amount relative to the total weight of the monomers constituting the component (A). Generally, it is in the range of about 0.1 to 2% by weight.

The component (A) obtained in this manner has a glass transition temperature of 0 to 100 ° C and a hydroxyl equivalent of 0.8 to 3.5 meq/g. Since such a component (A) can be well miscible with the component (B) and the component (C), the primer of the present invention is transparent and can be stored for a long period of time at room temperature. Moreover, by reacting such a component (A) with the component (B) and the component (C), the initial adhesion, wet heat resistance, whitening resistance, and transparent speckle resistance can be improved. From this viewpoint, the glass transition temperature of the component (A) is preferably about 25 to 80 ° C, and the hydroxyl equivalent is preferably about 1 to 2.5 meq/g.

Further, when the component (a3) is used in combination, in particular, when the whitening resistance is considered, the acid value of the component (A) is usually about 0.06 to 0.4 meq/g, preferably about 0.09 to 0.18 meq/g.

Further, the other physical properties of the component (A) are not particularly limited, and the weight average molecular weight is generally 3,000 from the viewpoints of initial adhesion, wet heat resistance, whitening resistance, and transparent speckle resistance of the primer. About 100,000, preferably about 10,000 to 80,000.

The component (B) is a composition comprising a reaction product of a triisocyanate (b1) (hereinafter also referred to as a component (b1)) and a glycol (b2) (hereinafter also referred to as a component (b2)).

As the component (b1), various known triisocyanates of a polymer which is a diisocyanate are preferable. Examples of the diisocyanate include aromatic diisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, and xylene diisocyanate; hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, and An aliphatic diisocyanate such as an amino acid diisocyanate; and an alicyclic ring such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated toluene diisocyanate; Diisocyanate. Further, examples of the polymer include isomeric cyanurate (1, 3, 5 - 3). -2,4,6-(1H,3H,5H)trione) or an adduct. Among them, a hetero-cyanurate body and/or an adduct of an aromatic diisocyanate is preferred from the viewpoint of moisture heat resistance, whitening resistance, and transparent speckle resistance.

Examples of the component (b2) include various known diols and/or water. Specific examples of the diol include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,3-butylene glycol, neopentyl glycol, 1,6-hexanediol, and octane. Glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol. Among them, in particular, from the viewpoint of adhesion to an aluminum thin film, an alkanediol (alkylene glycol) having a carbon number of 2 to 20 and/or water, more preferably an alkane having a carbon number of 2 to 8 is preferable. The diol and/or water is particularly preferably a 4-8 alkanediol and/or water.

The component (B) can be produced by various well-known amine esterification reactions. The ratio of use of the component (b1) and the component (b2) is not particularly limited, and in particular, from the viewpoint of adhesion to an aluminum film, generally, the isocyanate group (NCO') of the component (b1) and (b2) The equivalent ratio [NCO'/OH'] of the hydroxyl group (OH') of the diol in the component is generally in the range of about 5 to 20, preferably in the range of 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) is reacted with water molecules, and then a carbon dioxide (CO ₂ ↑) process is carried out to form a primary amine. Base (-NH ₂ ). The primary amine group then reacts with the NCO' group of the other (b1) component. Here, in this series of reactions, 1 mole of water molecules consume 2 moles of isocyanate groups of component (b1). Therefore, when water (H ₂ O) is used as the component (b2), the equivalent ratio [NCO'/OH'] is calculated by having two hydroxyl groups. At the time of the reaction, an organic solvent which does not react with the isocyanate group may be used as needed, for example, the ketone solvent, the glycol ether solvent, or the ester solvent.

The component (B) obtained in this manner is (B) from the viewpoints of mutual solubility, expiration date, initial adhesion, wet heat resistance, whitening resistance, and transparent speckle resistance of the primer of the present invention. The isocyanate group equivalent of the component is about 1 to 10 meq/g, preferably about 3 to 6 meq/g.

In the present invention, a triisocyanate or a hexafunctional polyisocyanate other than the component (b1) such as the diisocyanate or the isocyanuric acid triisocyanate may be optionally used (trade name "DURANATE MHG-80B", Asahi Kasei Chemical Co., Ltd. Made by the company, etc., used together with the component (B).

The ratio of use of the component (A) and the component (B) is not particularly limited, and in consideration of the mutual solubility or the use period of the primer of the present invention, in particular In view of whitening resistance and transparent speckle resistance, in general, the ratio of the hydroxyl equivalent of the component (A) to the isocyanate equivalent of the component (B) [NCO/OH] is in the range of about 1 to 6. Preferably, it is in the range of about 2 to 5.

As the component (C), various known epoxy group-containing ruthenium compounds can be used. Specific examples thereof include an epoxy group-containing alkoxydecane (c1) (hereinafter also referred to as a component (c1)) and/or an epoxy group-containing hemidecane oxide (c2) (hereinafter also referred to as ( C2) component), the component (c1) is represented by the formula (1), that is, X-Si(R ¹ ) _a (OR ² ) _3-a (in the formula (1), X represents an epoxy group. a hydrocarbon group having 1 to 8 carbon atoms, 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, a represents 0 or 1), and the component (c2) is such that (c1) The component is subjected to a hydrolysis reaction and a condensation reaction.

Examples of the component (c1) include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and 3-glycidoxypropyltri a glycidoxypropyltrialkoxydecane such as propoxydecane; and, 2-(3,4-epoxycyclohexyl)ethyltrimethoxynonane, 2-(3,4-epoxy group) Cyclohexyl)ethyltriethoxydecane, and 2-(3,4-epoxycyclohexyl)ethyltripropoxydecane (epoxycyclohexyl)ethyltrialkoxydecane, etc.; Two or more types of compounds can be used in combination.

In addition, when X in the above formula (1) is a compound such as an isocyanato group or a hydrocarbon group such as an alkyl group or a phenyl group, the component (c1) is substituted for the wet heat resistance, whitening resistance and resistance. The balance of transparent speckle is prone to poor.

The component (c2) is a hemidecane which is obtained by subjecting the component (c1) to a hydrolysis reaction and a condensation reaction. Further, in order to adjust the content of the epoxy group of the component (c2), in addition to the component (c1), the following compounds may be used as a raw material: methyltrimethoxydecane, methyltriethoxydecane, and B. An alkyltrial alkoxy oxane having no epoxy group, such as trimethoxy decane, ethyl triethoxy decane, phenyl trimethoxy decane, or phenyl triethoxy decane (hereinafter also referred to as (c1) ')ingredient).

In order to obtain the component (c2), first, the component (c1) and the component (c1') used as needed are subjected to a hydrolysis reaction. Specifically, for example, the component (c1) and the component (c1') used as needed may be subjected to a hydrolysis reaction in the presence of water and a catalyst. In addition, the amount of water is not particularly limited, and is generally the total of the alkoxy groups contained in [the number of moles of water used in the hydrolysis reaction] / [(c1) component and (c1 ') used as necessary. The molar number (mole ratio) is an amount of about 0.4 to 10, and preferably an amount of about 1. Further, examples of the catalyst include an acidic catalyst (a mineral acid such as hydrochloric acid, sulfuric acid or nitric acid; an organic acid such as formic acid or acetic acid) or a basic catalyst (1,8-diaza-bicyclo[5.4.0]undec-7. - an organic salt such as an olefin or 2-ethyl-4-methylimidazole; and an inorganic salt such as ammonia or sodium hydroxide), and the amount of the catalyst used is generally relative to the component (c1) and optionally The total weight of the component (c1') to be used is in the range of about 0.1 to 25% by weight, preferably about 1 to 10% by weight. The conditions of the hydrolysis reaction are also not particularly limited. Generally, 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.

Further, in the above hydrolysis reaction, the above organic solvent may be used, and in particular, the above alcohol solvent or glycol ether is suitable.

The target component (c2) is obtained by further subjecting the obtained hydrolysis reactant to a condensation reaction. The conditions of the condensation reaction are not particularly limited. Generally, the reaction temperature is about 40 to 150 ° C, preferably about 60 to 100 ° C, and the reaction time is about 30 minutes to 12 hours. Further, the above organic solvent can also be used in the condensation reaction.

The number of the component (c2) is not particularly limited, and examples thereof include [the number of unreacted hydroxyl groups and alkoxy groups in the (c2) component]/[(c1) component and the (c1') component used as necessary. The molar number of the alkoxy group originally contained is generally 0.3 or less, and the equivalent of the epoxy group is about 100 to 600 g/eq in terms of the solid content, and the nonvolatile content is about 50 to 90% by weight. Further, the residual alcohol, water, catalyst, solvent, and the like can be removed from the obtained component (c2) under reduced pressure as needed.

In addition, a partial condensate of a compound of the above formula (1) wherein X is a methoxy group such as a methoxy group or an ethoxy group or a hydrolyzate thereof, or various known cerium oxide particles are used instead (c2) The composition, the desired effect of the present invention, in particular, the initial adhesion of the primer, the heat and moisture resistance, the whitening resistance, and the transparent speckle resistance are difficult to achieve.

The amount of the component (C) is not particularly limited, and is generally from 3 to 20 parts by weight (calculated as solid content) based on 100 parts by weight (in terms of solid content) of the component (A) and the component (B). It is preferably about 5 to 15 parts by weight (calculated as solid content). If it is within this range, The primer, the wet heat resistance, the whitening resistance, and the transparent speckle resistance of the primer are particularly excellent.

The primer of the present invention is preferably used as a solution of the above component (D), and its solid component weight is usually about 5 to 50% by weight. Further, in the primer of the present invention, an amine esterification catalyst (such as a tin-based or tertiary amine-based catalyst), a Lewis acid catalyst, a leveling agent, an antioxidant, an ultraviolet absorber, or the like may be added or diluted. The aforementioned component (D) of the solvent.

The aluminum film-attached plastic of the present invention is a structure having various known plastic substrates (excluding plastic films), a layer composed of the primer of the present invention, and an aluminum film layer.

Examples of the plastic substrate include polyester (polyethylene terephthalate (PET), etc.), polyvinyl chloride, polyamide, polyimine, polycarbonate, and acrylonitrile-butadiene. - styrene copolymer (ABS), polyethylene, and polypropylene. Among them, polyester is preferred in view of adhesion to the undercoat layer and the like. Further, the shape of the plastic is not particularly limited, and may be, for example, a spherical shape, a cylindrical shape, a cylindrical shape, a rectangular parallelepiped shape, or a plate shape, and may have irregularities or curved surfaces.

The plastic film with an aluminum film of the present invention is a composite substrate having various known plastic films, a layer composed of the primer of the present invention, and an aluminum film layer.

Examples of the plastic film include a polyester film, a polyvinyl chloride film, a polyamide film, a polyimide film, a polycarbonate film, and a polyethylene film. And polypropylene film and the like. Among them, a polyester film is preferred in view of adhesion to the undercoat layer and the like.

Further, a functional layer such as a release layer, a hard coat layer, a fixing layer for a hard coat layer, or a pattern ink layer may be provided in advance on the plastic substrate and the plastic film.

The undercoat layer can be obtained by coating the primer of the present invention on the plastic substrate or the plastic film by various known coating means, and is generally at about 80 to 185 ° C. , heat and harden for 10 seconds to 5 minutes. The coating means is not particularly limited, and examples thereof include a sprayer, a roll coater, a reverse-roll coater, a gravure coater, and a doctor blade coating. A cloth machine, a bar coater, a dot coater, or the like. Further, the amount of the primer to be applied is not particularly limited, and is generally about 0.01 to 10 g/m ² in terms of dry solid content.

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

In the plastic film with aluminum film and the plastic film with aluminum film of the present invention, other functional layers may be provided depending on the use thereof. For example, the film is provided for use in a decorative film for in-mold forming or a decorative for insert molding. In the case of a film, a release layer, a hard coat layer, a fixing layer for a hard coat layer, a pattern ink layer, or the like may be provided between the plastic film layer and the undercoat layer. Further, an adhesive layer may be provided on the aluminum thin film layer.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the scope of the invention is not limited to these examples and comparative examples.

Moreover, "part" in the examples means a weight basis. In addition, the glass transition temperature is a value measured using a commercially available measuring instrument (trade name "DSC8230B", manufactured by Rigaku Corporation). The hydroxyl equivalent weight and the isocyanate group amount are calculated values calculated from the input amount of the raw material. In addition, the weight average molecular weight is a value measured by the commercially available gel permeation chromatography (trade name "HLC-8220GPC", manufactured by Tosoh Corporation). Further, the microscope photographs in the first to second figures were obtained by using a commercially available laser conjugated focus microscope (trade name "VK-9500", manufactured by Keyence Co., Ltd.).

<mixing (A) ingredients>

(Manufacturing Example 1)

In a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube, 192.0 parts of methyl methacrylate, 7.2 parts of n-butyl acrylate, and 40.8 parts of 2-hydroxyethyl acrylate were charged. And 360 parts of methyl ethyl ketone, and the reaction system was set to 80 °C. Then, 1.2 parts of azobisisobutyronitrile was charged and kept at around 80 ° C for 5 hours. Then, 2.4 parts of azobisisobutyronitrile was charged, and the reaction system was further kept at the same temperature for 4 hours. After that, the reaction system was cooled to room temperature. Thereafter, a solution of the acrylic copolymer (A-1) (30% nonvolatile content) was obtained, and the glass transition temperature was 70 ° C, the hydroxyl equivalent was 1.42 meq/g (hydroxyl price was 80 mgKOH/g), and The weight average molecular weight is 50,000.

(Manufacturing Example 2)

In the same reaction vessel as in Production Example 1, 189.6 parts of methyl methacrylate, 4.8 parts of n-butyl acrylate, 45.6 parts of 2-hydroxyethyl methacrylate, and 360.0 parts of methyl ethyl ketone were charged. And set the reaction system to 80 °C. Then, 1.2 parts of azobisisobutyronitrile was charged and kept at around 80 ° C for 5 hours. Then, 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 the acrylic copolymer (A-2) (30% nonvolatile content) was obtained, and the glass transition temperature was 90 ° C, and the hydroxyl equivalent was 1.42 meq/g ( The hydroxyl value was 80 mgKOH/g), and the weight average molecular weight was 50,000.

(Manufacturing Example 3)

In the same reaction vessel as in Production Example 1, 117.6 parts of methyl methacrylate, 81.6 parts of n-butyl acrylate, 40.8 parts of 2-hydroxyethyl acrylate, and 360.0 parts of methyl ethyl ketone were charged, and The reaction system was set to 80 °C. Then, 1.2 parts of azobisisobutyronitrile was charged and kept at around 80 ° C for 5 hours. Then, 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 the acrylic copolymer (A-3) (30% nonvolatile content) was obtained, and the glass transition temperature was 10 ° C, and the hydroxyl group was obtained. The equivalent weight was 1.42 meq/g (hydroxyl price was 80 mgKOH/g) and the weight average molecular weight was 55,000.

(Manufacturing Example 4)

In the same reaction vessel as in Production Example 1, 194.4 parts of methyl methacrylate, 14.4 parts of n-butyl acrylate, 31.2 parts of 2-hydroxyethyl acrylate, and 360.0 parts of methyl ethyl ketone were charged, and The reaction system was set to 80 °C. Then, 1.2 parts of azobisisobutyronitrile was charged and kept at around 80 ° C for 5 hours. Then, 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 the acrylic copolymer (A-4) (30% nonvolatile content) was obtained, and the glass transition temperature was 70 ° C, and the hydroxyl equivalent was 1.07 meq/g ( The hydroxyl value was 60 mgKOH/g), and the weight average molecular weight was 50,000.

(Manufacturing Example 5)

In the same reaction vessel as in Production Example 1, 201.6 parts of methyl methacrylate, 4.8 parts of n-butyl acrylate, 33.6 parts of 2-hydroxyethyl methacrylate, and 360.0 parts of methyl ethyl ketone were charged. And set the reaction system to 80 °C. Then, 1.2 parts of azobisisobutyronitrile was charged and kept at around 80 ° C for 5 hours. Then, 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 the acrylic copolymer (A-5) (30% nonvolatile content) was obtained, and the glass transition temperature was 90 ° C, and the hydroxyl equivalent was 1.07 meq/g ( The hydroxyl value was 60 mgKOH/g) and the weight average molecular weight was 52,000.

(Manufacturing Example 6)

In the same reaction vessel as in Production Example 1, 70.8 parts of methyl methacrylate, 84.0 parts of n-butyl acrylate, 64.8 parts of 2-hydroxyethyl acrylate, 20.4 parts of styrene, and 360.0 parts of A were charged. Base ethyl ketone and set the reaction system to 80 °C. Then, 1.2 parts of azobisisobutyronitrile was charged and kept at around 80 ° C for 5 hours. Then, 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 the acrylic copolymer (A-6) (30% nonvolatile content) was obtained, and the glass transition temperature was 0 ° C, and the hydroxyl equivalent was 2.31 meq/g ( The hydroxyl value was 130 mgKOH/g) and the weight average molecular weight was 55,000.

(Manufacturing Example 7)

In the same reaction vessel as in Production Example 1, 148.8 parts of methyl methacrylate, 60.0 parts of n-butyl acrylate, 31.2 parts of 2-hydroxyethyl acrylate, and 360.0 parts of methyl ethyl ketone were charged, and The reaction system was set to 80 °C. Then, 1.2 parts of azobisisobutyronitrile was charged and kept at around 80 ° C for 5 hours. Then, 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 the acrylic copolymer (A-7) (30% nonvolatile content) was obtained, and the glass transition temperature was 30 ° C, and the hydroxyl equivalent was 1.07 meq/g ( The hydroxyl value was 60 mgKOH/g), and the weight average molecular weight was 50,000.

(Manufacturing Example 8)

In the same reaction vessel as in Production Example 1, 166.8 parts of methyl methacrylate, 8.4 parts of n-butyl acrylate, 24.0 parts of stearyl acrylate, 40.8 parts of 2-hydroxyethyl acrylate, and 360.0 were charged. A portion of methyl ethyl ketone and the reaction system was set to 80 °C. Then, 1.2 parts of azobisisobutyronitrile was charged and kept at around 80 ° C for 5 hours. Then, 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 the acrylic copolymer (A-8) (30% nonvolatile content) was obtained, and the glass transition temperature was 60 ° C, and the hydroxyl equivalent was 1.42 meq/g ( The hydroxyl value was 80 mgKOH/g), and the weight average molecular weight was 53,000.

(Manufacturing Example 9)

In the same reaction vessel as in Production Example 1, 184.8 parts of methyl methacrylate, 7.2 parts of n-butyl acrylate, 40.8 parts of 2-hydroxyethyl acrylate, 7.2 parts of acrylic acid, and 360.0 parts of methyl group were charged. Ethyl ketone and the reaction system was set to 80 °C. Then, 1.2 parts of azobisisobutyronitrile was introduced, and the temperature was kept at 80 ° C for 5 hours. Then, 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 the acrylic copolymer (A-9) (30% nonvolatile content) was obtained, and the glass transition temperature was 70 ° C, and the hydroxyl equivalent was 1.42 meq/g ( The hydroxyl value was 80 mgKOH/g), the carboxyl group equivalent was 0.41 meq/g (acid value was 23 mgKOH/g), and the weight average molecular weight was 54,000.

(Manufacturing Example 10)

In the same reaction vessel as in Production Example 1, 184.8 parts of methyl methacrylate, 7.2 parts of n-butyl acrylate, 40.8 parts of 2-hydroxyethyl acrylate, 7.2 parts of methacrylic acid, and 360.0 parts were charged. Methyl ethyl ketone and the reaction system was set to 80 °C. Then, 1.2 parts of azobisisobutyronitrile was charged and kept at around 80 ° C for 5 hours. Then, 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 the acrylic copolymer (A-10) (30% nonvolatile content) was obtained, and the glass transition temperature was 70 ° C, and the hydroxyl equivalent was 1.42 meq/g ( The hydroxyl value was 80 mgKOH/g), the carboxyl group equivalent was 0.34 meq/g (acid value was 19 mgKOH/g), and the weight average molecular weight was 55,000.

(Comparative Manufacturing Example 1)

In the same reaction vessel as in Production Example 1, 177.6 parts of methyl methacrylate, 20.9 parts of n-butyl acrylate, 17.5 parts of 2-hydroxyethyl acrylate, 24.0 parts of styrene, and 360.0 parts of A were charged. Base ethyl ketone and set the reaction system to 80 °C. Then, 1.2 parts of azobisisobutyronitrile was charged and kept at around 80 ° C for 5 hours. Then, 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 the acrylic copolymer (i) (30% nonvolatile content) was obtained, and the glass transition temperature was 70 ° C, and the hydroxyl equivalent was 0.62 meq/g (hydroxyl price). It was 35 mgKOH/g) and had a weight average molecular weight of 45,000.

(Comparative Manufacturing Example 2)

In the same reaction vessel as in Production Example 1, 123.6 parts of methyl methacrylate, 16.8 parts of n-butyl acrylate, 99.6 parts of 2-hydroxyethyl acrylate, and 360.0 parts of methyl ethyl ketone were charged, and The reaction system was set to 80 °C. Then, 1.2 parts of azobisisobutyronitrile was charged and kept at around 80 ° C for 5 hours. Then, 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 the acrylic copolymer (ii) (30% nonvolatile content) was obtained, and the glass transition temperature was 30 ° C, and the hydroxyl equivalent was 3.56 meq/g (hydroxyl number). It was 200 mgKOH/g) and the weight average molecular weight was 48,000.

[Table 1]

MMA: Methyl methacrylate

nBA: n-butyl acrylate

SMA: stearyl acrylate

HEA: 2-hydroxyethyl acrylate

HEMA: 2-hydroxyethyl methacrylate

AA: Acrylic

MAA: Methacrylic acid

St: Styrene

<Mining (B) ingredients>

(Manufacturing Example 11)

In the same reaction vessel as in Production Example 1, 445.5 parts of a isocyanurate of toluene diisocyanate (trade name "CORONATE 2030", an isocyanate equivalent of 3.8 meq/g) and 5.0 parts of 1, were charged. 6-hexanediol and 308.6 parts of methyl ethyl ketone were subjected to an amine esterification reaction at 60 ° C for 3 hours. Thereafter, the mixture was cooled to room temperature, whereby an isocyanate composition (B-1) (isocyanate equivalent: 3.3 meq/g) was obtained.

(Manufacturing Example 12)

In the same reaction vessel as in Production Example 1, 445.5 parts of the above CORONATE 2030, 0.75 parts of water, 273.5 parts of methyl ethyl ketone, and 25.2 parts of propylene glycol monomethyl ether acetate were charged and operated at 60 ° C. The amine esterification reaction was carried out for 3 hours. Thereafter, the mixture was cooled to room temperature, whereby an isocyanate composition (B-2) (isocyanato group equivalent: 3.3 meq/g) was obtained.

<mixing (c2) ingredients>

In the same reaction vessel as in Production Example 1, 300 g of 3-glycidoxypropyltrimethoxydecane as a component (c1) (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM-403") was charged. 71.8 g of ion-exchanged water ([molar number of water used for hydrolysis reaction] / [total number of moles of alkoxy group contained in 3-glycidoxypropyltrimethoxydecane] (Moerby ) = 1.05), 1.5 g of 95% formic acid, 100 g of toluene, and subjected to a hydrolysis reaction at room temperature for 30 minutes. Further, [the molar number of the hydroxyl group produced by subjecting 3-glycidoxypropyltrimethoxydecane to hydrolysis reaction] / [3-glycidoxypropyltrimethoxy group] in the hydrolysis reaction The molar number of the alkoxy group originally contained in the decane] (mole ratio) was 0.9. After the hydrolysis reaction, the reaction system was heated to 70 ° C, at which time the methanol produced by the hydrolysis was distilled off to the outside of the reaction system. The water produced by the condensation reaction was distilled off by heating to 75 ° C for 30 minutes. Further, the mixture was reacted at 75 ° C for 30 minutes, and then 100 g of diethylene glycol dimethyl ether was added thereto, and the pressure was reduced while gradually reducing the pressure at 50 ° C for 3 hours to distill off residual methanol, water, formic acid, and toluene. Further, diethylene glycol dimethyl ether was added to adjust the solid content concentration to 15%, and a solution of 1500 g of an epoxy group-containing hemidecane oxide (c2) (hereinafter also referred to as a component (c2)) was obtained. The epoxy equivalent of (c2) was 1200 g/eq (180 g/eq in terms of solid content).

<mixing primer>

(Example 1)

10.0 parts of the component (A-1), 8.6 parts of the component (B-1) (NCO/OH = 2.0), and 0.56 parts of the epoxy group-containing alkoxydecane as the component (c1) (trade name " KBM-403", Shin-Etsu Chemical Industry Unit Prepared by Co., Ltd., and 10.6 parts of methyl ethyl ketone are thoroughly mixed to prepare a primer.

(Example 2)

10.0 parts of (A-2) component, 8.6 parts of (B-1) component (NCO/OH=2.0), 0.56 part of KBM-403, and 10.6 parts of methyl ethyl ketone were thoroughly mixed to prepare Primer.

(Example 3)

10.0 parts of (A-3) component, 8.6 parts of (B-1) component (NCO/OH=2.0), 0.56 part of KBM-403, and 10.6 parts of methyl ethyl ketone were thoroughly mixed to prepare Primer.

(Example 4)

10.0 parts of (A-4) component, 6.5 parts of (B-1) component (NCO/OH=2.0), 0.5 part of KBM-403, and 10.2 parts of methyl ethyl ketone are thoroughly mixed to prepare Primer.

(Example 5)

10.0 parts of (A-4) component, 6.5 parts of (B-1) component (NCO/OH=2.0), 0.5 part of KBM-403, and 10.2 parts of methyl ethyl ketone are thoroughly mixed to prepare Primer.

(Example 6)

10.0 parts of (A-6) component, 14.0 parts of (B-1) component (NCO/OH=2.0), 0.72 part of KBM-403, and 14.8 parts of methyl ethyl ketone were thoroughly mixed to prepare Primer.

(Example 7)

10.0 parts of (A-7) component, 6.5 parts of (B-1) component (NCO/OH=2.0), 0.5 part of KBM-403, and 10.2 parts of methyl ethyl ketone are thoroughly mixed to prepare Primer.

(Example 8)

10.0 parts of (A-8) component, 8.6 parts of (B-1) component (NCO/OH=2.0), 0.56 part of KBM-403, and 10.6 parts of methyl ethyl ketone were thoroughly mixed to prepare Primer.

(Example 9)

10.0 parts of (A-9) component, 8.6 parts of (B-1) component (NCO/OH=2.0), 0.56 part of KBM-403, and 10.6 parts of methyl ethyl ketone were thoroughly mixed to prepare Primer.

(Embodiment 10)

10.0 parts of (A-10) component, 8.6 parts of (B-1) component (NCO/OH=2.0), 0.56 part of KBM-403, and 10.6 parts of methyl ethyl ketone were thoroughly mixed to prepare Primer.

(Example 11)

10.0 parts of (A-1) component, 8.6 parts of (B-1) component (NCO/OH=2.0), 0.7 part of the component (c2) obtained in the above formulation, and 11.4 parts of methylethyl group The ketone is thoroughly mixed to formulate the primer.

(Embodiment 12)

(c2) obtained by using 10.0 parts of (A-1) component, 8.6 part of (B-1) component (NCO/OH=2.0), and 0.35 part of the above formulation example The composition and 10.7 parts of methyl ethyl ketone were thoroughly mixed to prepare a primer.

(Example 13)

10.0 parts of (A-1) component, 8.6 parts of (B-1) component (NCO/OH=2.0), 0.28 part of KBM-403, and 10.4 parts of methyl ethyl ketone were thoroughly mixed to prepare Primer.

(Example 14)

10.0 parts of (A-1) component, 8.6 parts of (B-1) component (NCO/OH=2.0), 0.84 part of KBM-403, and 12.6 parts of methyl ethyl ketone were thoroughly mixed to prepare Primer.

(Example 15)

10.0 parts of (A-1) component, 4.3 parts of (B-1) component (NCO/OH = 1.0), 0.21 part of KBM-403, and 8.3 parts of methyl ethyl ketone were thoroughly mixed to prepare Primer.

(Embodiment 16)

10.0 parts of (A-1) component, 12.8 parts of (B-1) component (NCO/OH=3.0), 0.34 part of KBM-403, and 12.7 parts of methyl ethyl ketone were thoroughly mixed to prepare Primer.

(Example 17)

10.0 parts of (A-1) component, 6.5 parts of (B-2) component (NCO/OH=2.0), 0.5 part of KBM-403, and 10.6 parts of methyl ethyl ketone are thoroughly mixed to prepare Primer.

(Comparative Example 1)

10.0 parts of (i) component, 3.8 parts of (B-1) component (NCO/OH=2.0), 0.42 part of KBM-403, and 8.6 parts of methyl ethyl ketone were thoroughly mixed to prepare a primer. Agent.

(Comparative Example 2)

10.0 parts of the component (ii), 10.7 parts of the component (B-1) (NCO/OH = 2.0), 0.63 parts of KBM-403, and 12.8 parts of methyl ethyl ketone were thoroughly mixed to prepare a primer. Agent.

(Comparative Example 3)

10.0 parts of (A-1) component, 8.6 parts of (B-1) component (NCO/OH=2.0), and 0.56 parts of 3-isocyanatopropyltriethoxylate for substituting (c1) component The base coater was prepared by thoroughly mixing the decane (trade name "KBE-9007", manufactured by Shin-Etsu Chemical Co., Ltd.) and 11.5 parts of methyl ethyl ketone.

(Comparative Example 4)

10.0 parts of (A-1) component, 8.6 parts of (B-1) component (NCO/OH=2.0), and 0.56 parts of ginseng (trimethoxydecylpropyl) which is substituted for the component (c1) The cyanurate (trade name "KBM-9659", manufactured by Shin-Etsu Chemical Co., Ltd.) and 11.5 parts of methyl ethyl ketone were thoroughly mixed to prepare a primer.

(Comparative Example 5)

10.0 parts of (A-1) component, 8.6 parts of (B-1) component (NCO/OH=2.0), and 0.56 parts of mercaptotrimethoxydecane (trade name "KBM" for substituting (c1) component -3103", Shin-Etsu Chemical Industry Unit Prepared by Co., Ltd., and 11.5 parts of methyl ethyl ketone are thoroughly mixed to prepare a primer.

(Comparative Example 6)

10.0 parts of the component (A-1), 8.6 parts of the component (B-1) (NCO/OH = 2.0), and 0.56 parts of a phenyltrimethoxydecane (trade name " used to substitute the component (c1) KBM-103", manufactured by Shin-Etsu Chemical Co., Ltd.), and 11.5 parts of methyl ethyl ketone were thoroughly mixed to prepare a primer.

(Comparative Example 7)

10.0 parts of (A-1) component, 8.6 parts of (B-1) component (NCO/OH=2.0), and 0.56 parts of methyltrimethoxydecane (product name) for substituting (c1) component KBM-13", manufactured by Shin-Etsu Chemical Co., Ltd.), and 11.5 parts of methyl ethyl ketone were thoroughly mixed to prepare a primer.

(Comparative Example 8)

10.0 parts of (A-1) component, 8.6 parts of (B-1) component (NCO/OH=2.0), and 0.56 parts of methyl decanoate oligomer (product name " used to replace (c1) component MKC Silicate MS-51", manufactured by Mitsubishi Chemical Corporation), and 11.5 parts of methyl ethyl ketone were thoroughly mixed to prepare a primer.

(Comparative Example 9)

10.0 parts of the component (A-1), 8.6 parts of the component (B-1) (NCO/OH = 2.0), and 1.86 parts of an organic cerium sol (organosilica sol, trade name "MEK" for substituting the component (c2) -ST", day The chemical industry co., Ltd.) and 10.2 parts of methyl ethyl ketone were thoroughly mixed to prepare a primer.

(Comparative Example 10)

A primer was prepared by thoroughly mixing 10.0 parts of the component (A-1), 7.5 parts of CORONATE 2030 (NCO/OH = 2.0), 0.68 parts of KBM-403, and 10.6 parts of methyl ethyl ketone.

<Making test panel>

On the polyethylene terephthalate film after the release treatment, a commercially available hard coating agent (trade name "ARONIX M305" was applied by a bar coater so that the film thickness after drying and hardening was 5 μm. It is a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, manufactured by Toagosei Co., Ltd., and is subjected to a hardening treatment at an illuminance of 100 mj/cm ² . Then, the primer of Example 1 was applied to the hard coat layer so that the dry film thickness became 1 μm, and the primer of Example 1 was applied.

Then, the obtained coating film was subjected to a hardening treatment (150 ° C, 60 seconds) by a downwind dryer. Then, a commercially available vapor deposition device (trade name "NS-1875-Z", manufactured by Nishiyama Seisakusho Co., Ltd.) was used for the coating film, and an aluminum vapor deposited film having a vapor deposition layer thickness of 50 nm was obtained.

Then, a vinyl chloride-vinyl acetate copolymer-based adhesive (trade name "Kanebirakku L-CM", manufactured by Kaneka Corporation) was applied to the vapor-deposited aluminum layer so that the dry film thickness was 1 μm. ). Then, the obtained coating film was dried (80 ° C, 10 seconds) in a downwind dryer. The coated film was thermally transferred onto a commercially available acrylic plate to be used as a test panel of Example 1. use. The primers of the other examples and comparative examples were also carried out in the same manner to produce test panels.

(starting adhesion)

Each of the test panels was cut into 100 squares with a utility knife on a hard-coated surface, and taped (trade name "CELLOTAPE (registered trademark)", manufactured by NICHIBAN Co., Ltd.), and strong. The ground was peeled off in the vertical direction, but the aluminum surface did not peel off. (represented as 5 in each table)

(wet heat adhesion)

The adhesion of each test panel after standing under constant temperature and humidity conditions of 65 ° C and 95% × 24 hours was evaluated in accordance with the same method as the above initial adhesion, and based on the following criteria.

5... Unable to confirm peeling.

4... A peel of less than 5% was confirmed on the aluminum surface.

3... It was confirmed that the peeling was 5% or more to less than 20% on the aluminum surface.

2... It was confirmed that the peeling was 20% or more to less than 50% on the aluminum surface.

1... 50% or more to 100% peeling was confirmed on the aluminum surface.

(whitening resistance)

After each test panel was placed under constant temperature and humidity conditions of 65 ° C and 95% × 24 hours, the whitening state was visually evaluated based on the following criteria.

5... No whitening occurred on the aluminum surface, and the metallic luster was maintained.

4... Some whitening occurs on the aluminum surface, but almost maintains the metallic luster.

3... Some whitening occurred on the aluminum surface as a whole, and it was observed that some metallic luster disappeared.

2... Strong whitening occurred on the aluminum surface as a whole, and the metallic luster disappeared.

1... The white surface is more strongly whitened and the metallic luster has completely disappeared.

(resistant to transparent speckle)

After the test panels were placed under constant temperature and humidity conditions of 65 ° C and 95% × 24 hours, the state of the transparent spots of the aluminum layer was visually evaluated based on the following criteria.

5... No transparent spots occurred on the aluminum surface.

4... Partially transparent spots appear on the aluminum surface.

3...Slightly transparent spots appear on the aluminum surface as a whole.

2... Most transparent spots occur on the aluminum surface as a whole.

1... Most large transparent spots occur on the aluminum surface as a whole.

[Table 2]

Claims (11)

A primer for plastics with an aluminum film, comprising: an acrylic copolymer (A) which is a hydroxyl group-free (meth)acrylic acid alkyl ester (a1) and a hydroxyl group-containing (meth)acrylic acid alkylene group The reactant of the ester (a2) has a glass transition temperature of 0 to 100 ° C and a hydroxyl equivalent of 0.8 to 3.5 meq/g; and an isocyanate composition (B) comprising a triisocyanate (b1) and a glycol and/or Or a reaction product of water (b2), and an isocyanate group equivalent of 1 to 10 meq/g; and an epoxy group-containing oxime compound (C) derived from an epoxy group-containing alkoxydecane (c1) and And / or an epoxy group-containing alkoxyoxane (c2) which is represented by the formula (1), that is, X-Si(R ¹ ) _a (OR ² ) _3-a represented by formula (1), X represents a carbon number of epoxy groups containing 1 to 8 hydrocarbon group, R ¹ represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, R ² is a C 1 - 8 The hydrocarbon group, a represents 0 or 1, and the epoxy group-containing semi-oxane (c2) is obtained by subjecting the epoxy group-containing alkoxydecane (c1) to a hydrolysis reaction and a condensation reaction. The primer according to claim 1, wherein the alkyl group of the component (a1) has a carbon number of from 1 to 20. The primer according to claim 1 or 2, wherein the hydroxyalkyl group of the component (a2) has a carbon number of 1 to 4. The primer according to any one of claims 1 to 3, wherein the component (b1) is a terpolymer of an aromatic diisocyanate, and the component (b2) is an alkanediol having 2 to 8 carbon atoms. The primer according to any one of claims 1 to 4, wherein the ratio of the hydroxyl equivalent of the component (A) to the isocyanate equivalent of the component (B) is NCO/OH of 1 to 6. The primer according to any one of claims 1 to 5, wherein the component (C) is used in an amount of 3 to 20 parts by weight based on 100 parts by weight of the total of the components (A) and (B). The primer according to any one of claims 1 to 6, wherein the primer is used as a solution of the organic solvent (D). A plastic film with an aluminum film, comprising: a plastic substrate, wherein the plastic film is excluded; a layer composed of the primer according to any one of claims 1 to 7; and an aluminum film layer. A plastic film with an aluminum film, which has a plastic film, a layer composed of the primer as described in any one of claims 1 to 7, and an aluminum film layer. A decorative film for in-mold forming, which is a plastic film with an aluminum film as described in claim 9 as a member. A decorative film for insert molding, which is a member having a plastic film with an aluminum film as described in claim 9.