TWI666275B - Primer for plastics with aluminum film, plastics with aluminum film and plastic film with aluminum film, decorative film for in-mold molding and decorative film for insert molding - Google Patents

Abstract

The problem of the present invention is to provide a novel primer, even if the plastic with an aluminum film is placed under high temperature and high humidity, the adhesion between the aluminum film and the plastic substrate will not be reduced, and the Whitening or transparent spots may occur.

In order to solve this problem, as the aforementioned primer, the present invention uses a composition containing a specific acrylic copolymer (A), which has a glass transition temperature of 0 to 100 ° C and a hydroxyl equivalent of 0.8 to 3.5 meq / g; isocyanate composition (B), which contains reactants of triisocyanates (b1) and diols and / or water (b2), and the isocyanate equivalent is 1 to 10 meq / g; and, contains epoxy -Based silicon compound (C), which is composed of a specific epoxy-containing alkoxysilane (c1) and / or an epoxy-containing silsesquioxane (c2). The oxyalkane (c2) is obtained by subjecting the epoxy group-containing alkoxysilane (c1) to a hydrolysis reaction and a condensation reaction.

Description

Primer for plastics with aluminum film, plastics with aluminum film, and aluminum Film plastic film, decorative film for in-mold molding, and decorative film for insert molding

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

An aluminum film-attached plastic is a film made of aluminum formed on the surface of a plastic substrate. In particular, plastics with an aluminum film having an aluminum film having a thickness of about several tens of nanometers in the surface area layer of the plastic film are appreciated and used as members for in-mold or insert molding decorative films, and can impart metal to the molded product In recent years, designs such as a sense of touch and a mirror sense have been provided for housings of various electronic products such as mobile phones and audio products, personal computers, and automotive interior parts.

In addition, in order to adhere an aluminum film to a plastic substrate, a primer containing various polymers as a main component is mostly used.

For example, Patent Document 1 describes a primer including a polyol and a polyisocyanate, the polyol having a specific glass transition temperature and Based on the hydroxyl equivalent, the adhesion between the plastic film and the aluminum film can be improved by the primer.

Further, Patent Document 2 describes a primer including an acrylic copolymer having a specific hydroxyl concentration and a polyisocyanate. The acrylic copolymer is composed of a specific alkyl (meth) acrylate and a hydroxyl-containing (meth) ). In addition, if this primer is used, not only the adhesion between the plastic film and the vapor-deposited aluminum film can be improved, but even if the plastic film with the aluminum film is placed at a high temperature, the aluminum film can not be whitened ( Whitening).

[Prior technical literature] (Patent Literature)

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

Patent Document 2: Japanese Patent Application Laid-Open 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, the following problems arise: the adhesion between the plastic substrate and the aluminum film is reduced, or the aluminum film A whitening part is generated on the surface.

In addition, when the plastic with an aluminum film of Patent Document 2 was placed under a high temperature and high humidity state, the following problem was found: as shown in FIG. 2, aluminum The film has many minute transparent portions (hereinafter also referred to as "transparent spots") and the like.

The problem of the present invention is to provide a novel primer, even under high temperature and high humidity, the adhesion of the aluminum film and the plastic substrate will not be reduced, and no whitening part or transparent spots will be generated on the aluminum film.

The inventor believes that the aforementioned "transparent spots" are formed by a certain reactant of aluminum and water, and they are transparent in the visible light region. Therefore, as shown in Fig. 2, they will appear to be on the aluminum film. Create countless tiny holes.

In addition, when researching a method that can solve the problem of transparent spots and maintain adhesion and whitening resistance, it was found that a specific epoxy group-containing silane compound was further added to a primer containing a specific acrylic polyol and a polyisocyanate. Thus, a primer can be obtained which can solve the aforementioned problems.

That is, the present invention relates to a primer for a plastic with an aluminum film, which comprises: an acrylic copolymer (A), which is a hydroxyl-free alkyl (meth) acrylate (a1) and a hydroxyl-containing Reactants of alkyl (meth) acrylates (a2), glass transition temperature is 0 to 100 ° C, and hydroxyl equivalent is 0.8 to 3.5 meq / g; isocyanate composition (B), which contains triisocyanates (b1) Reactants with diols and / or water (b2), and the isocyanate equivalent is 1 to 10 meq / g; and, the epoxy-containing silicon compound (C) is composed of epoxy-containing alkoxy Is composed of an alkylsilane (c1) and / or an epoxy-containing silsesquioxane (c2), and the epoxy-containing alkoxysilane (c1) is represented by the general formula (1), which is X-Si (R ¹ ) _a (OR ² ) _3-a (In the formula (1), X represents a hydrocarbon group having 1 to 8 carbons containing an epoxy group, R ¹ represents hydrogen or a hydrocarbon group having 1 to 8 carbons, and R ² represents A hydrocarbon group having 1 to 8 carbon atoms, a represents 0 or 1), and the epoxy group-containing silsesquioxane (c2) is a hydrolysis reaction and a condensation reaction of the epoxy group-containing alkoxysilane (c1) Made.

In addition, the present invention also relates to a plastic with an aluminum film, which includes a plastic substrate (except for a plastic film), a layer composed of the aforementioned primer, and an aluminum film layer.

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

The present invention also relates to a decorative film for in-mold molding and a decorative film for insert molding. These decorative films use the aforementioned plastic film with an aluminum film as a component.

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

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

Similarly, the plastic film with an aluminum film of the present invention has good initial adhesion, moisture and heat resistance, whitening resistance, and transparent speckle resistance. The plastic film with an aluminum thin film is suitable for, for example, a member for a decorative film for in-mold molding or insert molding, and is also suitable as a packaging material such as a gas barrier film, a transparent conductive sheet, and a film capacitor. capacitor), a labeling member.

FIG. 1 is a microscope photograph (400 times) of the vapor-deposited surface of the vapor-deposited aluminum PET film of Example 1. It is extremely smooth, and it can be seen that no transparent spots are generated.

FIG. 2 is a microscope photograph (400 times) of the vapor-deposited surface of the vapor-deposited aluminum PET film of Comparative Example 1. It can be seen that transparent spots have occurred on the vapor-deposited surface.

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

The component (A) is a copolymer in which a hydroxyl-free alkyl (meth) acrylate (a1) (hereinafter also referred to as (a1) component) and a hydroxyl-containing alkyl (meth) acrylate ( a2) (hereinafter also referred to as (a2) component).

The component (a1) 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 include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and secondary butyl (meth) acrylate. Ester, tertiary butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, dodecane (meth) acrylate Ester, stearyl (meth) acrylate, eicosyl (meth) acrylate, behenyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate , Cyclopentyl (meth) acrylate, isobornyl (meth) acrylate, and the like; these compounds can be used alone or in combination of two or more. Among these, an alkyl (meth) acrylate having about 1 to 20 carbon atoms in the alkyl group is preferred from the viewpoint of contributing particularly to the improvement of the transparent spot resistance of the primer of the present invention. Moreover, by using together (a1) component of carbon number of a different alkyl group, physical properties, such as the glass transition temperature of (A) component, can be adjusted.

The component (a2) is an indispensable monomer, and is not particularly limited as long as it is an (meth) acrylic acid alkyl ester having a hydroxyl group in the molecule. Various known (meth) acrylic acid alkyl esters can be used. The purpose is to impart a hydroxyl group to the component (A) and to react it with the components (B) and (C). Specifically, for example, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (formyl) Methyl) 3-hydroxybutyl acrylate, 4-hydroxybutyl (meth) acrylate, hydroxycyclohexyl (meth) acrylate, 4- (hydroxymethyl) cyclohexyl methyl (meth) acrylate, and 2- 4- (hydroxymethyl) cyclohexyl methyl hydroxypropionate Etc .; These compounds may be used singly or in combination of two or more kinds. Among them, from the viewpoints of the life of the primer of the present invention and the like, an alkyl (meth) acrylate having a carbon number of about 1 to 4 is preferred.

In addition, in the present invention, as the constituent monomers of the component (A), monomers (hereinafter also referred to as (a3) component) that do not conform to any of the components (a1) and (a2) 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 tertiary butylstyrene; 2,4,4-trimethyl-1-pentene, 3-methyl-1-butene, 3-methyl-1-pentene, 1 -Α-olefins such as hexene, vinylcyclohexane, and 2-methylvinylcyclohexane; (meth) allyl alcohol, 4-penten-1-ol, 1-methyl-3-butene Unsaturated alcohols such as -1-ol and 5-hexen-1-ol; phenyl (meth) acrylate, benzyl (meth) acrylate, and 4-methylbenzyl (meth) acrylate (formyl) Aryl) acrylate; dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylic acid Dialkylamino (meth) acrylates such as dimethylaminopropyl, diethylaminopropyl (meth) acrylate, and dimethylaminoethyl (meth) acrylic acid , Dialkylamines 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, Chain transfer monomers such as 2- (meth) acrylamido-2-methylpropanesulfonic acid, 2- (meth) acrylamidoamino-2-methylpropionic acid and salts thereof; vinylamine, ( Other monofunctional monomers, such as aminoethyl methacrylate, allyl mercaptan, and glycidyl (meth) acrylate; methylene bis (meth) acrylamide, ethylene bis (methyl ) Acrylamide and bis (meth) acrylamide such as hexamethylenebis (meth) acrylamide; ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate Isodi (meth) acrylates; divinyl adipate and divinyl sebacate; diallyldimethylammonium, diallyl phthalate, chlorobridged diene Difunctional monomers such as diallyl chlorendate and divinylbenzene; 1,3,5-tripropenyl hexahydro-s- three , Trifunctional monomers such as triallyl isocyanate, triallylamine, triallyl trimellitate, and N, N-diallyl allylamine; tetramethylolmethane Tetrafunctional monomers such as tetraacrylate, tetraallyl pyromellitic acid, and 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 acrylamide.

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

(a1) Composition: generally about 45 to 97 mole%, preferably about 65 to 90 mole%

(a2) Composition: generally about 3 ~ 45 mole%, preferably about 10 ~ 35 mole%

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

(a1) Composition: generally about 65 ~ 90 mole%, preferably about 70 ~ 85 mole%

(a2) Composition: generally about 5 to 35 mole%, preferably about 10 to 30 mole%

(a3) composition: generally about 1-20 mole%, preferably about 1-15 mole%

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 (D) component), generally in the presence of a radical polymerization initiator, at about 80 to 180 ° C, The (a1) component and the (a2) component and the aforementioned (a3) component used as necessary may be subjected to a copolymerization reaction 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, n-propanol, Low molecular alcohol solvents such as isopropanol and butanol; 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 and other glycol ether solvents; ethyl acetate, butyl acetate, methylcellulose acetate, and cellulose acetate solvents; Solvesso # 100 and Solvesso # 150 (both are trade names, manufactured by ExxonMobil) and other petroleum solvents; other chloroform and dimethylformamide The amount of the component (D) used is within a range of about 10 to 50% by weight of the solid content of the solution containing the component (A).

Examples of the radical polymerization initiator include hydrogen peroxide, ammonium persulfate, potassium persulfate, tert-butyl peroxybenzoate, dicumyl peroxide, lauryl peroxide, and 2,2 ' -Azobisisobutyronitrile and 2,2'-azobisisobutyric acid dimethyl, etc .; the amount of the radical polymerization initiator used is 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 way has a glass transition temperature of 0 to 100 ° C and a hydroxyl equivalent of 0.8 to 3.5 meq / g. Such (A) component can be mutually miscible with (B) component and (C) component. Therefore, the primer of the present invention is transparent and can be stored at room temperature for a long time. Furthermore, by reacting such (A) component with (B) component and (C) component, the said initial adhesiveness, moist heat-resistant adhesiveness, whitening resistance, and transparent spot resistance can be made favorable. 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.

In addition, when the aforementioned (a3) component is used in combination, especially in consideration of whitening resistance, the acid value of the (A) component is generally about 0.06 to 0.4 meq / g, and preferably about 0.09 to 0.18 meq / g.

In addition, other physical properties of the component (A) are not particularly limited, and the weight average molecular weight is generally 3,000 to 3,000 from the viewpoints of the initial adhesion, moisture and 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 containing a reactant of a triisocyanate (b1) (hereinafter also referred to as (b1) component) and a diol (b2) (hereinafter also referred to as (b2) component).

The component (b1) is preferably a triisocyanate of various known polymers that are diisocyanates. Examples of the diisocyanate include aromatic diisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, and xylene diisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and ionomers. Aliphatic diisocyanates such as urethane diisocyanate; and alicyclic systems such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated toluene diisocyanate Diisocyanate. Examples of the polymer include isotricyanate (1,3,5-tri -2,4,6- (1H, 3H, 5H) trione) or adducts. Among these, an isotricyanate body and / or an adduct of an aromatic diisocyanate is preferable from the viewpoint of moist heat resistance, whitening resistance, and transparent speckle resistance.

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

The component (B) can be produced by various known amine esterification reactions. The use ratio of the (b1) component and the (b2) component is not particularly limited. In particular, from the viewpoint of adhesion to an aluminum thin film, generally, the isocyanate (NCO ') and (b2) The equivalent ratio [NCO '/ OH'] of the hydroxyl groups (OH ') of the diols in the component) is generally in a range of about 5 to 20, and preferably in a range of about 10 to 20. On the other hand, when water (H ₂ O) is used as the (b2) component, the isocyanate group of the (b1) component reacts with water molecules and then undergoes a process of removing carbon dioxide (CO ₂ ↑) to form a primary amine. Radical (-NH ₂ ). This primary amine group will then react with the NCO 'group of the other (b1) component. Here, during this series of reactions, 1 mol of water molecules will consume 2 mol of the isocyanate group (b1). Therefore, when water (H ₂ O) is used as the component (b2), the equivalent ratio [NCO '/ OH'] is calculated as if it has two hydroxyl groups. During the reaction, an organic solvent that does not react with an isocyanate group may be used as necessary, such as the aforementioned ketone-based solvent, glycol ether-based solvent, and ester-based solvent.

The component (B) obtained in this way is, from the viewpoint of the mutual solubility or useful life of the primer of the present invention, the initial adhesion, the heat and moisture resistance, the whitening resistance, and the transparent speckle resistance. The isocyanate equivalent of the component) is about 1 to 10 meq / g, preferably about 3 to 6 meq / g.

In addition, in the present invention, as needed, the triisocyanate and hexafunctional polyisocyanate (brand name "DURANATE MHG-80B") other than the aforementioned diisocyanate or lysine triisocyanate (b1), asahi Kasei Chemicals Co., Ltd. Used by the company).

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

As the component (C), various known epoxy-group-containing silicon compounds can be used. Specifically, for example, an epoxy-group-containing alkoxysilane (c1) (hereinafter also referred to as a (c1) component) and / or an epoxy-group-containing hemisiloxane (c2) (hereinafter also referred to as ( c2) component), the (c1) component is represented by the general formula (1), that is, X-Si (R ¹ ) _a (OR ² ) _3-a (in formula (1), X represents an epoxy group-containing A hydrocarbon group having 1 to 8 carbons, R ¹ represents a hydrogen or a hydrocarbon group having 1 to 8 carbons, R ² represents a hydrocarbon group having 1 to 8 carbons, a represents 0 or 1), and the (c2) component is such that (c1 ) Ingredients are made by hydrolysis reaction and condensation reaction.

Examples of the (c1) component include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropyltrisilane Glycidoxypropyltrialkoxysilanes such as propoxysilane; and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxy Cyclohexyl) ethyltriethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltripropoxysilane (epoxycyclohexyl) ethyltrialkoxysilane; etc .; these The compound may be used in combination of two or more kinds.

Furthermore, if a compound in which X in the general formula (1) is an isocyanate group or a hydrocarbon group such as an alkyl group and a phenyl group is used instead of the component (c1), the moisture and heat resistance, whitening resistance, and resistance The balance of the transparent speckle is easily deteriorated.

The component (c2) is a type of siloxane, which is obtained by subjecting the component (c1) to a hydrolysis reaction and a condensation reaction. In addition, in order to adjust the epoxy group content of the component (c2), in addition to the component (c1), the following compounds may be used as raw materials: methyltrimethoxysilane, methyltriethoxysilane, ethyl Alkyltrialkoxysilanes (hereinafter also referred to as (c1) which do not contain epoxy groups such as trimethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, and phenyltriethoxysilane ')ingredient).

To obtain the (c2) component, first, the (c1) component and the (c1 ') component used as necessary are subjected to a hydrolysis reaction. Specifically, for example, the component (c1) and the component (c1 ') used as required 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 [mol number of water used in the hydrolysis reaction] / [(c1) component and (c1 ') used as necessary Molar number] (Molar ratio) is an amount of about 0.4 to 10, preferably an amount of about 1. Examples of the catalyst include acid catalysts (inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as formic acid and acetic acid) or basic catalysts (1,8-diaza-bicyclo [5.4.0] undec-7. -Organic salts such as alkenes, 2-ethyl-4-methylimidazole; and inorganic salts such as ammonia and sodium hydroxide), and the amount of the catalyst used is generally, relative to (c1) the component and The total weight of the component (c1 ') used is in the range of about 0.1 to 25% by weight, and preferably in the range of 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.

In the hydrolysis reaction, the organic solvent may be used, and in particular, the alcohol-based solvent or glycol ether is suitable.

The target (c2) component is obtained by further subjecting the obtained hydrolysis reaction product to a condensation reaction. The conditions for 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. In the condensation reaction, the aforementioned organic solvent may be used.

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

In addition, in place of (c2), a partial condensate of a compound in which X in the general formula (1) is an alkoxy group such as a methoxy group or an ethoxy group or a hydrolyzate thereof, or various known silica particles is used. ) Component, the desired effect of the present invention, especially the initial adhesion, moisture and heat resistance, whitening resistance, and transparent speckle resistance of the primer described above, it will be difficult to achieve a balance.

(C) The amount of the component to be used is not particularly limited. Generally, it is about 3 to 20 parts by weight (in terms of solid content) relative to 100 parts by weight (in terms of solid content) of the components (A) and (B). It is preferably about 5 to 15 parts by weight (in terms of solid content conversion). If it is within this range, it will The initial adhesiveness, moisture and heat resistance, whitening resistance, and transparent speckle resistance of the primer are particularly good.

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

The aluminum film-attached plastic of the present invention is a structure having various well-known plastic substrates (except 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, polyimide, polyimide, polycarbonate, and acrylonitrile-butadiene. -Styrene copolymer (ABS), polyethylene, and polypropylene. Among these, polyester is preferable in view of adhesion to the undercoat layer and the like. 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 unevenness or a curved surface.

The aluminum film-attached plastic 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 polyimide film, a polyimide film, a polycarbonate film, a polyethylene film, And polypropylene film. Among these, a polyester film is preferable in view of adhesion to the undercoat layer and the like.

Furthermore, the plastic substrate and the plastic film may be provided with functional layers such as a release layer, a hard coating layer, a fixing layer for a hard coating layer, and a pattern ink layer in advance.

The undercoat layer can be obtained by coating the undercoating agent of the present invention on the aforementioned plastic substrate or the aforementioned plastic film by various well-known coating methods, and generally at about 80 to 185 ° C. Let it heat harden for about 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. Cloth machine, bar coater, dot coater, etc. The coating amount of the primer is not particularly limited, and generally, it is 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 aluminum seeds on the hardened undercoat layer by various known thin film forming methods. Examples of the thin film formation method include various physical methods (vacuum thermal evaporation, sputtering, etc.) and chemical methods (chemical vapor phase reaction, etc.). The thickness of the aluminum thin film layer is not particularly limited, but is generally about 5 to 500 nm, and preferably about 5 to 50 nm.

In the plastic film with an aluminum film and the plastic film with an aluminum film according to the present invention, other functional layers may be provided depending on the application. For example, the film is provided with a decoration film for in-mold molding or a decoration for insert molding. When filming, between the plastic film layer and the undercoat layer, a release layer, a hard coating layer, a fixing layer for a hard coating layer, and a pattern ink layer can be provided. An adhesive layer may be provided on the aluminum thin film layer.

[Example]

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

In addition, "part" in an Example shows a basis of weight. The glass transition temperature is a value measured using a commercially available measuring instrument (trade name "DSC8230B", manufactured by Rigaku Denki Co., Ltd.). The hydroxyl equivalent and the amount of isocyanate are calculated values calculated from the input amount of the raw materials. The weight average molecular weight is a value measured using a commercially available gel permeation chromatography (trade name "HLC-8220GPC", manufactured by Tosoh Corporation). The microscope photographs in Figs. 1 and 2 were taken using a commercially available laser conjugate focal microscope (trade name "VK-9500", manufactured by Keyence Corporation).

<Mixing (A) Ingredient>

(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 put in and kept at 80 ° C. for 5 hours. Then, 2.4 parts of azobisisobutyronitrile was added, and the reaction system was further kept at the same temperature for about 4 hours. After that, the reaction system was cooled to room temperature as Then, a solution of the acrylic copolymer (A-1) (non-volatile content: 30%) was obtained, the glass transition temperature was 70 ° C, 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 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 put in and kept at 80 ° C. for 5 hours. Then, 2.4 parts of azobisisobutyronitrile was added, and the reaction system was further kept at the same temperature for about 4 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution of the acrylic copolymer (A-2) (non-volatile content: 30%). 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.

(Manufacture 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 put in and kept at 80 ° C. for 5 hours. Then, 2.4 parts of azobisisobutyronitrile was added, and the reaction system was further kept at the same temperature for about 4 hours. Thereafter, the reaction system was cooled to room temperature, thereby obtaining a solution of the acrylic copolymer (A-3) (non-volatile content: 30%), the glass transition temperature of which was 10 ° C., and the hydroxyl group. The equivalent weight was 1.42 meq / g (hydroxyl value 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 put in and kept at 80 ° C. for 5 hours. Then, 2.4 parts of azobisisobutyronitrile was added, and the reaction system was further kept at the same temperature for about 4 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution of the acrylic copolymer (A-4) (non-volatile content: 30%). 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 put in and kept at 80 ° C. for 5 hours. Then, 2.4 parts of azobisisobutyronitrile was added, and the reaction system was further kept at the same temperature for about 4 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution of the acrylic copolymer (A-5) (non-volatile content: 30%). 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 formic acid were charged. Ethyl ketone, and the reaction system was set to 80 ° C. Then, 1.2 parts of azobisisobutyronitrile was put in and kept at 80 ° C. for 5 hours. Then, 2.4 parts of azobisisobutyronitrile was added, and the reaction system was further kept at the same temperature for about 4 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution of the acrylic copolymer (A-6) (non-volatile content: 30%). 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 put in and kept at 80 ° C. for 5 hours. Then, 2.4 parts of azobisisobutyronitrile was added, and the reaction system was further kept at the same temperature for about 4 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution of the acrylic copolymer (A-7) (non-volatile content: 30%). 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. Parts of methyl ethyl ketone, and the reaction system was set to 80 ° C. Then, 1.2 parts of azobisisobutyronitrile was put in and kept at 80 ° C. for 5 hours. Then, 2.4 parts of azobisisobutyronitrile was added, and the reaction system was further kept at the same temperature for about 4 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution of the acrylic copolymer (A-8) (non-volatile content: 30%). 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 Ethyl ketone, and the reaction system was set to 80 ° C. Then, 1.2 parts of azobisisobutyronitrile was put in, and the temperature was kept at about 80 ° C. for 5 hours. Then, 2.4 parts of azobisisobutyronitrile was added, and the reaction system was further kept at the same temperature for about 4 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution of the acrylic copolymer (A-9) (non-volatile content: 30%). The glass transition temperature was 70 ° C, and the hydroxyl equivalent was 1.42 meq / g ( The hydroxyl value is 80 mgKOH / g), the carboxy equivalent is 0.41 meq / g (the acid value is 23 mgKOH / g), and the weight average molecular weight is 54000.

(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 of Methyl ethyl ketone, and the reaction system was set to 80 ° C. Then, 1.2 parts of azobisisobutyronitrile was put in and kept at 80 ° C. for 5 hours. Then, 2.4 parts of azobisisobutyronitrile was added, and the reaction system was further kept at the same temperature for about 4 hours. Thereafter, the reaction system was cooled to room temperature, thereby obtaining a solution of the acrylic copolymer (A-10) (non-volatile content: 30%). The glass transition temperature was 70 ° C, and the hydroxyl equivalent was 1.42 meq / g ( The hydroxyl value is 80 mgKOH / g), the carboxy equivalent is 0.34 meq / g (the acid value is 19 mgKOH / g), and the weight average molecular weight is 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 formic acid were charged. Ethyl ketone, and the reaction system was set to 80 ° C. Then, 1.2 parts of azobisisobutyronitrile was put in and kept at 80 ° C. for 5 hours. Then, 2.4 parts of azobisisobutyronitrile was added, and the reaction system was further kept at the same temperature for about 4 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution of the acrylic copolymer (i) (non-volatile content: 30%). The glass transition temperature was 70 ° C, and the hydroxyl equivalent was 0.62 meq / g (hydroxyl value It was 35 mgKOH / g), and the weight average molecular weight was 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 put in and kept at 80 ° C. for 5 hours. Then, 2.4 parts of azobisisobutyronitrile was added, and the reaction system was further kept at the same temperature for about 4 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution of the acrylic copolymer (ii) (non-volatile content: 30%). The glass transition temperature was 30 ° C, and the hydroxyl equivalent was 3.56 meq / g (hydroxyl value 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

<Composition (B) component>

(Manufacturing example 11)

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

(Manufacturing example 12)

In the same reaction vessel as in Production Example 1, 445.5 parts of the aforementioned 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 the reaction was carried out at 60 ° C. The amine was esterified for 3 hours. Then, it cooled to room temperature, and obtained the isocyanate composition (B-2) (isocyanate group equivalent 3.3 meq / g).

<Composition (c2) component>

In the same reaction vessel as in Production Example 1, 300 g of 3-glycidoxypropyltrimethoxysilane (component of "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 Molar number of alkoxy groups contained in 3-glycidoxypropyltrimethoxysilane] (Molar ratio ) = 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. In addition, in the hydrolysis reaction, [the number of moles of the hydroxyl group generated by the hydrolysis reaction of 3-glycidoxypropyltrimethoxysilane] / [3-glycidoxypropyltrimethoxy The mole number (molar ratio) of alkoxy groups originally contained in silane is 0.9. After the hydrolysis reaction, the temperature of the reaction system was raised to 70 ° C. At this time, the methanol produced by the hydrolysis began to be distilled out of the reaction system. It took 30 minutes to raise the temperature to 75 ° C. to distill off water generated by the condensation reaction. After further reacting at 75 ° C. for 30 minutes, 100 g of diethylene glycol dimethyl ether was added, and the pressure was gradually reduced while reducing the pressure at 50 ° C. for 3 hours to remove the remaining methanol, water, formic acid, and toluene. Further, diethylene glycol dimethyl ether was added so that the solid content concentration became 15%, and a solution of 1500 g of an epoxy-containing silsesquioxane (c2) (hereinafter also referred to as (c2) component) was obtained. The epoxy equivalent of (c2) was 1200 g / eq (180 g / eq in terms of solid content conversion).

<Preparation of Primer>

(Example 1)

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

(Example 2)

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

(Example 3)

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

(Example 6)

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

(Example 8)

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

(Example 9)

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

(Example 10)

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

(Example 11)

10.0 parts of the component (A-1), 8.6 parts of the (B-1) component (NCO / OH = 2.0), 0.7 part of the (c2) component obtained in the aforementioned preparation example, and 11.4 parts of methyl ethyl The ketone is thoroughly mixed to prepare a primer.

(Example 12)

(C2) obtained by mixing 10.0 parts of the component (A-1), 8.6 parts of the component (B-1) (NCO / OH = 2.0), and 0.35 parts of the aforementioned preparation example The ingredients and 10.7 parts of methyl ethyl ketone were sufficiently mixed to prepare a primer.

(Example 13)

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

(Example 14)

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

(Example 15)

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

(Example 16)

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

(Example 17)

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

(Comparative example 1)

Mix 10.0 parts of (i) component, 3.8 parts of (B-1) component (NCO / OH = 2.0), 0.42 parts of KBM-403, and 8.6 parts of methyl ethyl ketone to prepare a base coat. Agent.

(Comparative example 2)

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

(Comparative example 3)

10.0 parts of the (A-1) component, 8.6 parts of the (B-1) component (NCO / OH = 2.0), and 0.56 parts of the 3-isocyanatopropyltriethoxy group used to replace the (c1) component Silane (trade name "KBE-9007", manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and 11.5 parts of methyl ethyl ketone were sufficiently mixed to prepare a primer.

(Comparative Example 4)

10.0 parts of the component (A-1), 8.6 parts of the (B-1) component (NCO / OH = 2.0), and 0.56 parts of the parameter (trimethoxysilylpropyl) used to replace the (c1) component A cyanurate (trade name "KBM-9659", manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and 11.5 parts of methyl ethyl ketone were sufficiently mixed to prepare a primer.

(Comparative example 5)

10.0 parts of the (A-1) component, 8.6 parts of the (B-1) component (NCO / OH = 2.0), and 0.56 parts of the decyltrimethoxysilane (brand name "KBM") used to replace the (c1) component -3103 ", Shin-Etsu Chemical Industry Co., Ltd. Co., Ltd.) and 11.5 parts of methyl ethyl ketone were mixed thoroughly to prepare a primer.

(Comparative Example 6)

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

(Comparative Example 7)

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

(Comparative Example 8)

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

(Comparative Example 9)

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

(Comparative Example 10)

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 were thoroughly mixed to prepare a primer.

<Production of test panel>

A commercially available hard coating agent (trade name: "ARONIX M305") was applied to the polyethylene terephthalate film after the release treatment so that the film thickness after drying and curing became 5 μm. "Is a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, manufactured by Toa Synthesis Co., Ltd.), and is hardened at an illumination of 100 mj / cm ² . Next, the undercoat agent of Example 1 was applied on a hard coat layer with a bar coater so that the dry film thickness became 1 μm.

Then, the obtained coating film was hardened with a downwind dryer (150 degreeC, 60 second). Then, a commercially available vapor deposition device (trade name "NS-1875-Z", manufactured by Nishiyama Seisakusho Co., Ltd.) was used for this coating film to obtain a vapor-deposited aluminum film having a thickness of 50 nm.

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

(Initial adhesion)

For each test panel, 100 squares were cut with a utility knife on a hard-coated surface, and an adhesive tape (trade name "CELLOTAPE (registered trademark)", manufactured by NICHIBAN Co., Ltd.) was applied and strong. The floor was peeled in the vertical direction, but the aluminum surface was not peeled. (Represented as 5 in each table)

(Damp heat adhesion)

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

5 ... Peeling cannot be confirmed.

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

3 ... Peeling of more than 5% to less than 20% was confirmed on the aluminum surface.

2 ... A peeling of more than 20% to less than 50% was confirmed on the aluminum surface.

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

(Albino resistance)

Each test panel was placed under the conditions of constant temperature and humidity of 65 ° C. and 95% × 24 hours, and then the whitening state was visually evaluated according to the following criteria.

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

4 ... Slight whitening occurred on the aluminum surface, but the metallic luster was almost maintained.

3 ... Slight whitening occurred on the entire aluminum surface, and some metallic luster was observed to disappear.

2 ... Strong whitening occurred on the entire aluminum surface, and the metallic luster disappeared.

1 ... More intense whitening occurs on the entire aluminum surface, and the metallic luster has completely disappeared.

(Transparent speckle resistance)

After placing each test panel under the conditions of constant temperature and humidity of 65 ° C. and 95% × 24 hours, the transparent spot state of the aluminum layer was visually evaluated according to the following criteria.

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

4 ... Partial transparent spots occur on the aluminum surface.

3 ... Slightly transparent spots occur on the entire aluminum surface.

2 ... Most transparent spots occur on the entire aluminum surface.

1 ... Most large transparent spots occur on the entire aluminum surface.

[Table 2]

Claims (11)

An aluminum film-attached primer for plastics, comprising: an acrylic copolymer (A), which is a hydroxyl-free alkyl (meth) acrylate (a1) and a hydroxyl-containing (meth) acrylate The ester (a2) reactant has a glass transition temperature of 0 to 100 ° C and a hydroxyl equivalent weight of 0.8 to 3.5 meq / g. The isocyanate composition (B) includes a triisocyanate (b1) and a diol and / Or a reactant of water (b2), and the isocyanate equivalent is 1 to 10 meq / g; and, the epoxy-containing silicon compound (C) is composed of an epoxy-containing alkoxysilane (c1) and / Or epoxy-containing siloxanes (c2), the epoxy-containing alkoxysilane (c1) is represented by the general formula (1), which is X-Si (R ¹ ) _a (OR ² ) Is represented by _3-a . In the formula (1), X represents a hydrocarbon group having 1 to 8 carbons containing epoxy groups, R ¹ represents hydrogen or a hydrocarbon group having 1 to 8 carbons, and R ² represents 1 to 8 carbons. Hydrocarbon group, a represents 0 or 1, and the epoxy group-containing hemisiloxane (c2) is obtained by subjecting the epoxy group-containing alkoxysilane (c1) to a hydrolysis reaction and a condensation reaction. The primer according to claim 1, wherein the carbon number of the alkyl group of the component (a1) is 1 to 20. The primer according to claim 1 or 2, wherein the carbon number of the hydroxyalkyl group of the component (a2) is 1 to 4. The primer according to claim 1, 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 claim 1, wherein the ratio of the hydroxyl equivalent of the component (A) to the isocyanate equivalent of the component (B), that is, NCO / OH is 1 to 6. The primer according to claim 1, wherein the use amount of the component (C) is 3 to 20 parts by weight based on 100 parts by weight of the total of the component (A) and the component (B). The primer according to claim 1, wherein the primer is used as a solution of an organic solvent (D). An aluminum film-attached plastic has: a plastic substrate, except for the plastic film; a layer composed of the primer according to any one of claims 1 to 7; and an aluminum film layer. An aluminum film-attached plastic film has a plastic film, a layer composed of the primer according to any one of claims 1 to 7, and an aluminum film layer. A decorative film for in-mold forming is a plastic film with an aluminum thin film as described in claim 9 as a component. A decorative film for insert molding is a plastic film with an aluminum film as described in claim 9 as a component.