JP2011195835A - Undercoating agent for plastic with inorganic thin film, plastic with inorganic thin film, decorative film for in-mold molding and decorative film for insert molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel undercoating agent for plastics with an inorganic thin film that can form an undercoat layer which is excellent in adhesion to both a plastic substrate and an inorganic thin film layer (hereinafter referred to as adhesion), can retain smoothness of the surface of the inorganic thin film (hereinafter referred to as smoothness), will not cause a whitening phenomenon on the surface of the inorganic thin film even when used under a high temperature environment (hereinafter referred to as whitening resistance) and will not cause a craze or crack such as can be visually judged and interference fringe at the site to be processed on the inorganic thin film even when subjected to mold-processing under a high temperature (hereinafter referred to as processing resistance).SOLUTION: The undercoating agent includes (A) an acrylic copolymer having a carboxylate anion group and having a glass transition temperature of -5 to 120°C and (B) a polyaziridine compound having at least three aziridinyl groups.

Description

  The present invention relates to an undercoat agent used for bringing an inorganic thin film layer and a plastic substrate into close contact, a plastic with an inorganic thin film obtained using the undercoat agent, and an in-mold using the plastic with an inorganic thin film as a member. The present invention relates to a decorative film for molding and a decorative film for insert molding.

  A plastic with an inorganic thin film is generally formed on the surface of a molded (structural) or film plastic substrate made of a metal such as gold, copper, aluminum or tin, or a metal oxide such as silicon oxide. Conventionally, depending on the chemical species forming the inorganic thin film, the thickness of the thin film, etc., conventional packaging materials such as bottles, caps and retort packs, packaging materials such as gas barrier films, transparent conductive sheets, film capacitors, displays It is used for various purposes such as labeling.

  In addition, among plastics with inorganic thin films, aluminum-deposited plastic films having an extremely thin aluminum layer of about several tens of nanometers formed by vapor-depositing aluminum on the surface of plastic films are used as decorative film (also called transfer foil) members. In recent years, for example, it has been applied to the casings of various electronic products such as mobile phones, audio products, personal computers, etc. It is provided.

  A method of forming an inorganic thin film on a flexible undercoat layer by pre-coating an undercoat agent mainly composed of various polymers on the surface of a plastic substrate when producing a plastic with an inorganic thin film Has been adopted. This is because it is difficult to ensure the adhesion between the inorganic thin film layer and the plastic substrate and the smoothness of the inorganic thin film because there are usually fine irregularities and impurities (plastic additives, etc.) on the surface of the plastic substrate. Because. Insufficient adhesion causes peeling of the inorganic thin film, etc. In addition, when the smoothness is insufficient, especially when the inorganic thin film is made of metal, the gloss is impaired, and thus design is particularly required. It becomes a problem in use.

  Further, in the field of decorative films, in recent years, a method of simultaneously performing molding and transfer in a high-temperature environment, such as a so-called in-mold molding method, has been generalized. Cracks or cracks may occur in the part, and so-called whitening phenomenon such as fogging or blurring may occur on the glossy surface. Such cracks and the like are a serious problem because they cause interference fringes (rainbow fringes) of visible light even if they are minute ones that cannot be visually judged. Further, the whitening phenomenon is strongly required to be improved in a field where design properties are required, such as a decorative film.

  For example, in Patent Document 1, it is known that the above-described problems such as cracks can be solved by a three-pack type undercoat agent containing an acrylic resin, a melamine resin, and a polyisocyanate compound. However, the whitening phenomenon is referred to. It has not been. Conventionally, polyurethane resins and polyester resins have been awarded as the base resin for the anchor coating agent. However, when such an undercoat agent is used, the appearance of the inorganic thin film surface becomes poor, and the above-mentioned whitening and cracking have occurred. It is difficult to solve such problems.

JP 2004-122456 A

  The present invention is excellent in adhesion between the plastic substrate and the inorganic thin film layer (hereinafter referred to as adhesion), can maintain the smoothness of the inorganic thin film surface (hereinafter referred to as smoothness), and is used under a high temperature environment. Does not cause a whitening phenomenon on the surface of the inorganic thin film (hereinafter referred to as whitening resistance), and does not cause cracks, cracks, or interference fringes that can be visually judged in the inorganic thin film at the processing site even during molding at a high temperature. It is an object of the present invention to provide a novel undercoat agent for plastic with an inorganic thin film capable of forming an undercoat layer (hereinafter referred to as process resistance).

  As a result of extensive studies, the present inventor has found that the above problems can be solved by the following undercoat agent. That is, the present invention relates to an undercoat for plastic with an inorganic thin film, which contains an acrylic copolymer (A) having a carboxylate anion group and a glass transition temperature of -5 to 120 ° C and a polyaziridine compound (B) having at least three aziridinyl groups. Agent: Plastic with inorganic thin film having a plastic substrate, a layer made of the undercoat agent, and a layer made of an inorganic thin film; a decorative film for in-mold molding using the plastic with the inorganic thin film as a member; The present invention relates to a decorative film for insert molding as a member.

  Since the undercoat agent of the present invention is excellent in film formability, a smooth inorganic thin film can be formed on the plastic surface. In particular, when the inorganic thin film is a metal thin film such as aluminum, an inorganic thin film surface excellent in gloss can be obtained. Moreover, since the undercoat layer made of the undercoat agent has good adhesion to both the plastic substrate and the inorganic thin film layer, peeling of the inorganic thin film is reduced when handling the plastic with the inorganic thin film.

  In addition, the plastic with an inorganic thin film using the undercoat agent is excellent in whitening resistance, such as being difficult to cause whitening phenomenon such as fogging and blurring in the inorganic thin film even when placed in a high temperature environment. Further, even when subjected to molding at high temperature, the inorganic thin film is excellent in process resistance, such as interference fringes and cracks or cracks that can be visually judged are difficult to occur.

  Therefore, the said plastic with an inorganic thin film is suitable as a member of packaging containers, such as a bottle, a cap, a retort pack, a gas barrier film, a transparent conductive sheet, a film capacitor, a display label, and a decoration film, for example. In addition, the film-like plastic with an inorganic thin film is excellent in crack resistance and whitening resistance of the inorganic thin film layer, and therefore is particularly subjected to insert molding decorative film members and molding processing at high temperatures. It is suitable as a member of a decorative film for in-mold molding.

Appearance of evaporated aluminum film with workability evaluation of 6 (electron micrograph (3000 times)) Appearance of evaporated aluminum film with workability evaluation of 5 (electron micrograph (3000 times)) Appearance of aluminum deposited film with workability evaluation of 4 (electron micrograph (3000 times)) Appearance of aluminum deposited film with workability evaluation of 3 (electron micrograph (3000 times)) Appearance of evaporated aluminum film with workability evaluation of 2 (electron micrograph (3000 times)) Appearance of aluminum deposited film with workability evaluation of 1 (electron micrograph (3000 times))

  The undercoat agent according to the present invention includes an acrylic copolymer (A) having a glass transition anion group and a glass transition temperature of −5 to 120 ° C. (hereinafter referred to as “component (A)”), a polyaziridine compound having at least three aziridinyl groups. It contains (B) (hereinafter referred to as component (B)) and, if necessary, an aziridinyl group ring-opening catalyst (C) (hereinafter referred to as component (C)).

As the component (A), various known compounds can be used without particular limitation as long as they are acrylic copolymers having the glass transition temperature and having a carboxylate anion group (—COO ⁻ ) in the molecule.

  As a preferred embodiment of the component (A), α, β-unsaturated carboxylic acid (a1) (hereinafter referred to as component (a1)), (meth) acrylic acid alkyl ester and / or styrenes (a2) (hereinafter referred to as ( a2) component) and, if necessary, a neutralized copolymer obtained by reacting an unsaturated monomer (a3) other than these (hereinafter referred to as component (a3)). In this case, the carboxylate anion group of the component (A) is derived from the carboxyl group that the component (a1) has.

  Examples of the component (a1) include α, β-unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and isocrotonic acid, and α, β-unsaturated dicarboxylic acids such as fumaric acid and (anhydrous) maleic acid. Examples thereof include monoesters of acid, the α, β-unsaturated dicarboxylic acid and alcohols described later.

  Examples of the component (a2) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, lauryl (meth) acrylate, and (meth) acrylic. Stearyl acid, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, isobornyl (meth) acrylate, etc. Can be mentioned. Moreover, the alkyl group of the component (a2) does not have an active hydrogen-containing group such as a hydroxyl group, and the carbon number is usually about 1 to 20, preferably about 1 to 8, and more preferably 1 to 5. Examples of styrenes include styrene, α-methylstyrene, t-butylstyrene, dimethylstyrene, and the like.

  Examples of the component (a3) include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and (meth) acrylic acid. Such as 4-hydroxybutyl, hydroxycyclohexyl (meth) acrylate, 4- (hydroxymethyl) cyclohexylmethyl (meth) acrylate, 4- (hydroxymethyl) cyclohexylmethyl 2-hydroxypropionate, hydroxyphenyl (meth) acrylate, etc. Hydroxy (meth) acrylates; acrylamide, methacrylamide, N- (2-hydroxyethyl) acrylamide, N- (1-methyl-2-hydroxyethyl) acrylamide, (meth) acrylamides; unsaturated sulfonic acids; Killed unsaturated monomers; polyoxyalkylene unsaturated monomers; chlorosilane (meth) acrylates; (poly) siloxane mono (meth) acrylates; fluoroalkyl (mono) acrylates .

  Although the use mol% of (a1) component and (a2) component is not specifically limited, Usually, it is about 7-70 mol% and about 30-93 mol% in order, Preferably it is 13-45 mol%, 55-87 mol %. In addition, when the component (a3) is used, the use mol% of the components (a1) to (a3) is usually about 7 to 70 mol%, about 29 to 92 mol%, and about 1 to 60 mol% in order. , Preferably 13 to 45 mol%, 52 to 84 mol%, 3 to 20 mol%.

  Although the manufacturing method of (A) component is not specifically limited, For example, the said (a1) component-(a3) component are about 1 to 20 hours at about 80-180 degreeC normally in presence of a polymerization initiator and an organic solvent. A method of neutralizing the obtained polymer with a neutralizing agent after radical polymerization can be employed.

  As polymerization initiators, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) Etc.

  Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, butyl alcohol, and ethylene glycol; glycol ethers such as ethylene glycol monoethyl ether and ethylene glycol mono n-normal propyl ether; ethylene Examples include glycol ether esters such as glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and ethylene glycol mono n-propyl ether acetate, ketones such as acetone and methyl ethyl ketone, and dimethylformamide.

  Examples of neutralizing agents include ammonia; primary amines such as monomethylamine, monoethylamine, monobutylamine, and cyclohexylamine; secondary amines such as dimethylamine and diethylamine; tertiary amines such as trimethylamine and triethylamine; Examples include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide. Among these, it is particularly preferable to use ammonia and / or tertiary amines because whitening resistance, workability, and the like are improved. The amount of the neutralizing agent used is usually in the range of about 80 to 300 mol% with respect to the carboxyl group of the acrylic copolymer.

  The component (A) has a glass transition temperature of -5 to 120 ° C, preferably 40 to 110 ° C, mainly from the viewpoint of whitening resistance and workability. The glass transition temperature is a measured value. Further, the content of the carboxylate anion group of the component (A) is not particularly limited, but is usually about 0.5 to 8 mmol / g, preferably 1 to 5 mmol / g. There is a tendency that the property and workability are improved. The “content of carboxylate anion group” refers to the number of moles of carboxylate anion group contained in 1 g of component (A) (in terms of non-volatile content) and is a calculated value.

  The weight average molecular weight of component (A) (polystyrene conversion value by gel permeation chromatography) is not particularly limited, but is usually about 3000 to 100,000, preferably 10,000 to 80,000 mainly from the viewpoint of whitening resistance and processability. .

  As the component (B), various known compounds (see US Pat. No. 4,382,135, JP-A-2003-104970, etc.) can be used without particular limitation as long as they have at least three aziridinyl groups in the molecule. Specifically, compounds represented by the following general formula are preferable.

(In the formula, X ¹ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, R ¹ represents hydrogen or a methyl group, and R ² and R ³ represent hydrogen or carbon number, respectively. Represents an alkyl group of 1-6.)

  Examples of the compound represented by the formula include tetramethylolmethane-tri- (β-aziridinylpropionate), trimethylolpropane tris (β-aziridinylpropionate), and glyceryltris (β-aziridinini). Lupropionate) and the like.

  Examples of the other component (B) include tetraaziridin compounds such as tetraaziridinyl metaxylenediamine, tetraaziridinylmethylparaxylenediamine, and pentaerythritol tetra (β-aziridinylpropionate).

  Further, together with the component (B), neopentyl glycol di (β-aziridinylpropionate), 4,4′-isopropylidenediphenoldi (β-aziridinylpropionate), 4,4′-methylene Diaziridine compounds such as diphenoldi (β-aziridinylpropionate) and mono-such as 2-methylaziridine, 2-ethylaziridine, 2,2-dimethylaziridine, 2,3-dimethylaziridine, 2-phenylaziridine An aziridine compound can be used in combination.

  The content of the aziridinyl group of the component (B) is not particularly limited, but is usually in the range of about 3 to 11 mmol / g, preferably 5 to 9 mmol / g, particularly considering whitening resistance and workability. . The “content of aziridinyl group” means the number of moles of aziridinyl group contained in 1 g of component (B), and is a calculated value.

  The component (C) can be used as necessary particularly for the purpose of improving whitening resistance and workability. Specific examples include acid catalysts such as p-toluenesulfonic acid, hydrochloric acid, bromic acid, iodic acid, fluoric acid, fluorosulfonic acid, sulfuric acid, phosphoric acid, and diaryl iodonium salts, triarylsulfonium salts, diarylphosphonium salts, and the like. It is done. In these, since it is easy to handle, an acid catalyst, especially para-toluenesulfonic acid is preferable. Moreover, the said neutralizing agent, Preferably ammonia can be used with (C) component as needed. The neutralizing agent can be used as an aqueous solution.

  The undercoat agent of the present invention can be obtained by mixing the component (A), the component (B) and, if necessary, the component (C) by various known methods. The content ratio of the component (A) and the component (B) is not particularly limited. However, particularly from the viewpoint of whitening resistance and workability, the content of the carboxylate anion group of the component (A) (mmol / g) × gram of component (A) used (g) (non-volatile content)] / [content of aziridinyl group of component (B) (mmol / g) × gram of component used (g) (non-volatile content) Conversion)] is usually about 0.01 to 10, preferably 0.1 to 2. Moreover, although the usage-amount of (C) component is not specifically limited, Usually, it is about 1-15 weight% in conversion of solid content with respect to (B) component, Preferably it is the range used as 5-10 weight%.

  The undercoat agent of the present invention can be used as a solution using the organic solvent or water (ion exchange water or the like) as a solvent. As the organic solvent, the alcohols and glycol ethers are preferable. When both an organic solvent and water are used, the weight ratio is usually about 9/1 to 1/9 in order.

  The nonvolatile content of the undercoat agent of the present invention is not particularly limited, but is usually about 5 to 50% by weight. In addition, the amount of the component (A), the component (B), and the component (C) in the nonvolatile content is usually about 42 to 85% by weight, about 15 to 58% by weight, and about 0 to 8% by weight. .

  In addition to the undercoat agent of the present invention, additives such as a leveling agent, an antioxidant, an ultraviolet absorber, colloidal silica, and a filler can be blended.

  The plastic with an inorganic thin film of the present invention has a plastic substrate, a layer made of the undercoat agent of the present invention, and a layer made of an inorganic thin film.

  Examples of the plastic substrate include polyester, polyvinyl chloride, polyamide, polyimide, polycarbonate, polyethylene, and polypropylene, and these may be subjected to surface treatment such as corona discharge. In addition, the plastic substrate is a spherical body, a cylindrical body, a rectangular parallelepiped shape, a plate-like structure (excluding those corresponding to a plastic film), or a film shape, and there are unevenness and a curved surface on a part of the surface. It may be. The thickness of the film-like plastic substrate is not particularly limited, but is usually about 12 to 200 μm.

  Examples of the seed forming the inorganic thin film include metals such as aluminum, gold, silver, palladium, and tin, and metal oxides such as aluminum oxide, tin oxide, indium tin oxide, titanium oxide, and silicon oxide, and these can be used in combination. .

The method for producing the plastic with an inorganic thin film of the present invention is not particularly limited. For example, after applying the coating agent of the present invention to the plastic substrate by various known methods, the undercoat layer is cured (processing conditions: Usually, about 60 to 165 ° C., about 10 seconds to 5 minutes), and then a method of forming the inorganic thin film seed on the undercoat surface. Examples of the coating method for the undercoat agent include spray, roll coater, reverse roll coater, gravure coater, knife coater, bar coater, and dot coater. The coating amount is not particularly limited, but is usually about 0.01 to 10 g / m ² as a nonvolatile content. Examples of means for forming the inorganic thin film include various known physical methods (vacuum thermal evaporation, sputtering, etc.) and chemical methods (chemical vapor phase reaction, etc.). The thickness of the inorganic thin film is usually about 5 to 800 nm.

  In the plastic film with an inorganic thin film, another functional layer may be adjacent to each of the plastic film layer, the undercoat layer, and the inorganic thin film layer depending on the application. For example, when the plastic film with an inorganic thin film of the present invention is used for a decorative film for in-mold molding, a release layer, a hard coat layer, an anchor layer for a hard coat layer, a pattern between the plastic film and the undercoat layer An ink layer or the like may be present. An adhesive layer may be present on the inorganic thin film layer.

  Among the plastics with an inorganic thin film of the present invention, those in which the plastic substrate is in the form of a film (plastic film with an inorganic thin film) are particularly useful as a member of a decorative film for in-mold molding or a decorative film for insert molding. . In this case, the plastic substrate is preferably a polyester film, and the inorganic thin film layer is preferably an aluminum layer and / or a tin layer of about 5 to 50 nm.

  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 thereto. Further, “parts” in the examples represent weight standards.

  In each example, the glass transition temperature is a value obtained using a commercially available measuring instrument (product name “DSC8230B”, manufactured by Rigaku Corporation). The number average molecular weight is a value measured using a commercially available gel permeation chromatography instrument (product name “HLC-8220GPC”, manufactured by Tosoh Corporation).

<Manufacture of (A) component>
Production Example 1
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, a commercially available carboxyl group-containing styrene acrylic copolymer (product name “ARUFON-UC3920”, manufactured by Toagosei Co., Ltd., nonvolatile content 100 %, (A1) component is acrylic acid, (a2) component is styrene) 500.0 parts, isopropyl alcohol (hereinafter referred to as IPA) 150.0 parts, ion-exchanged water (hereinafter referred to as IW) 2055.6 parts, 28 % Aqueous ammonia (hereinafter referred to as 28% NH ₃ ) 155.8 parts, and kept at 45 ° C. for 3 hours, the glass transition temperature (hereinafter referred to as Tg) is 104 ° C., the content of carboxylate anion group (A-1) component having 4.3 mmol / g (hereinafter referred to as CA) and a weight average molecular weight (hereinafter referred to as Mw) of 15500. A liquid (nonvolatile content (hereinafter referred to as NV) of 20%) was obtained.

Production Example 2
In the same reaction vessel as in Production Example 1, 16.8 parts of methacrylic acid (hereinafter referred to as MAA), 151.2 parts of methyl methacrylate (hereinafter referred to as MMA), 2-hydroxyethyl methacrylate (hereinafter referred to as 2-HEA). 72 parts, 1.2 parts of 2,2′-azobis (2-methylbutyronitrile) (hereinafter referred to as ABN-E) and 360 parts of IPA were charged at 80 ° C. under nitrogen gas flow, The time was maintained (pre-polymerization step). Subsequently, 2.4 parts of ABN-E was charged, and the reaction system was further kept at the same temperature for 3 hours (the post-polymerization step). Next, 288.2 parts of IPA, 288.2 parts of IW, and 23.6 parts of triethylamine (hereinafter referred to as TEA) were charged and neutralized (the neutralization and dilution steps). Table 1 shows the physical properties of the component (A-2) thus prepared.

Production Examples 3-6, Comparative Production Examples 1-3
The components (A-3) to (A-6) and the comparative (AC-1) component to (AC-3) were prepared in the same manner as in Production Example 2 except that the raw materials in the number of parts shown in Table 1 were used. ) Each component solution was obtained. The respective physical properties are shown in Table 1.

AA: Acrylic acid BA: Normal butyl acrylate 28% NH ₃ : 28% ammonia water

Comparative production example 4
A reaction vessel similar to Production Example 1 was charged with 479 parts of terephthalic acid, 402 parts of isophthalic acid, 87 parts of azelaic acid, 256 parts of ethylene glycol, 354 parts of 1,6-hexanediol, and 23 parts of glycerin, and the reaction system was stirred. Were heated to melt them. Next, while removing water produced by the dehydration condensation reaction, the reaction system was heated from 160 ° C. to 200 ° C. over 3 hours, and further kept at 200 ° C. for 1 hour. Next, 0.16 part of antimony trioxide was added. Next, a vacuum decompression device was connected to the reaction vessel, and a reduced pressure polycondensation reaction was performed at 235 ° C. and 2.8 kPa for 1 hour. Next, the reduced pressure state was released, the reaction system was cooled to 150 ° C., 119 parts of trimellitic anhydride was charged into the reaction system, and the temperature was kept for 1 hour. Next, 1997 parts of methyl isobutyl ketone and 1997 parts of methyl ethyl ketone were added and dissolved uniformly to obtain a solution of polyester resin (PE-1) having a Tg of 19 ° C., CA of 0.4 mmol / g and Mw of 30000 (NV of 35 % By weight).

Comparative Production Example 5
In a reaction vessel similar to Production Example 1, 362.3 parts of a commercially available polycarbonate diol (product name “Nipporan 980R”, number average molecular weight 2000; manufactured by Nippon Polyurethane Industry Co., Ltd.), 151.4 parts of isophorone diisocyanate, 2, 2 -36.3 parts of dimethylol propionic acid and 550 parts of methyl ethyl ketone were prepared, and urethanation reaction was performed at 80 degreeC for 10 hours, and 1100 parts of urethane prepolymers of the isocyanate group terminal were obtained. The prepolymer was then stirred into a chain extender solution (24.6 parts triethylamine, 41.1 parts isopropyl alcohol, 3.6 parts isophoronediamine, 12.1 parts adipic acid dihydrazide, 434.9 parts methyl ethyl ketone). The whole reaction system was mixed. Thereafter, the reaction system is stirred and held at 60 ° C. for 2 hours to complete the chain extension reaction, whereby a polyurethane resin (PU-1) having a Tg of −10 ° C., a CA of 0.5 mmol / g, and an Mw of 14000 is obtained. An aqueous solution (NV 35% by weight) was obtained.

<Manufacture of undercoat agent>
Example 1
(A-1) 5 parts of component, tetramethylolmethane-tri- (β-aziridinylpropionate) (product name “TAZO”, manufactured by Mutual Yakuhin Co., Ltd., content of aziridinyl group 7 mmol / g) (Hereinafter referred to as TAZO) 1.2 parts, paratoluenesulfonic acid (hereinafter referred to as PTS) 0.12 parts, 28% NH ₃ 0.04 parts, IPA 8.4 parts, IW 8.4 Partly mixed in a beaker to prepare a coating agent with NV of 10% by weight.

Examples 2 to 15 and Comparative Examples 1 to 43
A coating agent was prepared in the same manner as in Example 1 except that the raw materials in the number of parts shown in each table were used.

PZ-33: Trimethylolpropane tris (β-aziridinylpropionate) (product name “Chemite PZ-33”, manufactured by Nippon Shokubai Co., Ltd., content of aziridinyl group: 7 mmol / g)
SV-02: Carbodiimide curing agent (trade name “Carbodilite SV-02”, Nisshinbo Chemical Co., Ltd., carbodiimide group content 2.3 mmol / g)
WS-700: Oxazoline-based curing agent (trade name “Epocross WS-700”, manufactured by Nippon Shokubai Co., Ltd., content of oxazoline group: 4.5 mmol / g)
EX-612: Epoxy curing agent (trade name “Denacol”, manufactured by Nagase ChemteX Corporation, epoxy group content 5.9 mmol / g)
(A) / (B): [(A) component carboxylate anion group content (mmol / g) × (A) component usage gram (g) (in terms of non-volatile content)] / [(B) component Content of aziridinyl group (mmol / g) × gram of use of component (g) (g) (nonvolatile content conversion)]

<Production and evaluation of aluminum vapor-deposited plastic film>
The undercoat agent obtained in Example 1 was applied to a commercially available PET film (product name “E5100”, manufactured by Toyobo Co., Ltd., 38 μm thickness) using a bar coater so that the dry film thickness would be 1 μm. Then, the coated film was dried (150 ° C., 60 seconds) with a circulating dryer.

  Next, the obtained dry film is set in a commercially available vapor deposition apparatus (product name “NS-1875-Z”, manufactured by Nishiyama Seisakusho Co., Ltd.) to obtain an aluminum vapor deposition film having a vapor deposition layer thickness of 50 nm. It was. This was used as the test film of Example 1. Test films were prepared in the same manner for other examples and comparative examples.

(appearance)
The appearance of the vapor deposition surface of the test film according to Example 1 was visually evaluated according to the following criteria. Test films according to other examples and comparative examples were similarly evaluated. The results are shown in Tables 4 and 5.
3 ... No whitening occurs on the vapor deposition surface 2 ... A slight whitening occurs on the entire vapor deposition surface 1 ... Strong whitening or interference fringes occur on the entire vapor deposition surface

(Adhesion)
An adhesive tape (product name “Cello Tape (registered trademark)”, manufactured by Nichiban Co., Ltd.) was attached to the vapor deposition surface of the test film according to Example 1, and was peeled off in a vertical direction. Moreover, it evaluated similarly about the test film which concerns on another Example and a comparative example. In any case, peeling did not occur in the aluminum vapor deposition film, so in Tables 4 and 5, all were set to 3.

(Whitening resistance) The external appearance of the vapor deposition surface after heating the test film which concerns on Example 1 for 60 minutes with a 150 degreeC circulating air dryer was visually evaluated on the following references | standards. The results are shown in Tables 4 and 5.
4 ... No whitening or interference fringes occur on the aluminum deposition surface 3 ... Whitening partially occurs on the aluminum deposition surface, but no interference fringes occur 2 ... Whitening or interference fringes slightly on the entire aluminum deposition surface 1 ... Strong whitening and interference fringes occur on the entire surface of the aluminum deposition surface

(Processability)
The undercoat agent obtained in Example 1 was applied to a commercially available acrylic panel (product name “Comoglas”, manufactured by Kuraray Co., Ltd., 5 cm × 5 cm × 1 mm) with a bar coater so that the dry film thickness was 1 μm. Then, a test panel for workability test was prepared by drying at 150 ° C. for 60 seconds in a smooth air dryer. Test panels were similarly prepared for the undercoat agents according to other examples and comparative examples.

  Further, as an instrument for bending the test panel, an aluminum plate (15 cm × 5 cm × 1 mm) bent at 60 ° in the middle was prepared.

  Next, the bending instrument is taken out after being heated in a smooth air dryer (250 ° C.), and the test panel is pressed from the acrylic panel side on the bending side of the instrument in a high temperature state for about 3 seconds, and then about 80 °. After being bent, the state of the aluminum vapor deposition surface at the bent portion was visually evaluated according to the following criteria. Moreover, it evaluated similarly about the test panel which concerns on another Example and a comparative example. The results are shown in Tables 4 and 5.

6: There is no cracking or peeling at the aluminum deposition site, no cloudiness or interference fringes are observed, and the appearance is better than 5 by visual judgment. 5: There is no cracking or peeling at the aluminum deposition site, and No cloudiness or interference fringes are observed 4 ... No cracking or peeling at the aluminum deposition site, and slight fogging is observed, and no interference fringes are found 3 ... No cracking or peeling at the aluminum deposition site, and Slight cloudiness and interference fringes are observed 2. Fine cracks and peeling are observed at the aluminum deposition site, and 1 Haze and interference fringes are strongly observed 1. Large cracks and peeling are observed at the aluminum deposition site, and Cloudiness and interference fringes are strongly recognized

  By using a thick acrylic panel, the undercoat surface (layer) is excessively stretched in the panel bending direction. As a result, the aluminum vapor deposition layer is more likely to crack. These harsh test conditions are intended for actual in-mold injection molding.

Examples 16-20, Comparative Examples 44-46
<Production and evaluation of tin-deposited plastic film>
The undercoat agent obtained in Example 1 was applied to the PET film using a bar coater so that the dry film thickness was 1 μm, and then the coated film was dried in a circulating dryer (150 ° C. 60 seconds). Next, a tin vapor deposition film having a vapor deposition layer thickness of 50 nm was obtained using the vapor deposition device. Similarly, the tin-deposited films were obtained for the undercoat agents of Examples 8, 11, 13, 15 and Comparative Examples 29, 31, and 33. Next, the smoothness, adhesion, whitening resistance, and processability of each film were evaluated according to the methods and criteria of the test items described above. The results are shown in Table 6.

Claims (12)

An undercoat agent for plastic with an inorganic thin film, comprising an acrylic copolymer (A) having a carboxylate anion group and a glass transition temperature of -5 to 120 ° C and a polyaziridine compound (B) having at least three aziridinyl groups. Component (A) is an α, β-unsaturated carboxylic acid (a1), (meth) acrylic acid alkyl ester and / or styrene (a2), and if necessary, an unsaturated monomer other than these (a3) The undercoat agent according to claim 1, wherein the copolymer obtained by reacting is neutralized. The undercoat agent of Claim 1 or 2 whose carboxylate anion group of (A) component is 0.5-8 mmol / g. (A) The undercoat agent in any one of Claims 1-3 whose weight average molecular weights of component are 3000-100000. (B) The undercoat agent in any one of Claims 1-4 whose component is represented by the following general formula.
(In the formula, X ¹ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, R ¹ represents hydrogen or a methyl group, and R ² and R ³ represent hydrogen or carbon number, respectively. Represents an alkyl group of 1-6.) Furthermore, the undercoat agent in any one of Claims 1-5 containing an aziridinyl group ring-opening catalyst (C). The undercoat agent according to claim 6, wherein the component (C) is paratoluenesulfonic acid. The content ratio of component (A) and component (B) is [content of carboxylate anion group of component (A) (mmol / g) × gram of component (g) used (g) (non-volatile content)] / [Content of aziridinyl group of component (B) (mmol / g) × Used gram of component (g) (in terms of non-volatile content)] is in the range of 0.01-10. 7. Any undercoat agent according to 7. A plastic with an inorganic thin film comprising a plastic substrate, a layer made of the undercoat agent according to any one of claims 1 to 8, and a layer made of an inorganic thin film. The plastic with an inorganic thin film according to claim 9, wherein the plastic substrate is in a film form. The decorative film for in-mold shaping | molding which uses the plastic with an inorganic thin film of Claim 10 as a member. The decorative film for insert molding which uses the plastic with an inorganic thin film of Claim 10 as a member.