JP2016104853A - Undercoat agent for plastic with aluminum thin film, plastic with aluminum thin film, plastic film with aluminum 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 undercoat agent that does not reduce adhesiveness between an aluminum thin film and a plastic substrate even when placing plastic with an aluminum thin film under high temperature and high humidity and does not generate a whitening part or lacking on a surface of the aluminum thin film.SOLUTION: There is provided an undercoat agent for plastic with an aluminum thin film containing (A) a specific acryl copolymer having glass transition temperature of 0 to 100°C and hydroxyl group equivalent of 0.8 to 3.5 meq/g, (B) an isocyanate composition containing a reaction product of triisocyanates (b1) and diols (b2) and having isocyanate group equivalent of 1 to 10 meq/g and (C) a polymer consisting of a hydroxyl group-containing acryl silicone resin (c1) and/or a hydroxyl group-containing fluorine resin (c2).SELECTED DRAWING: None

Description

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

  The plastic with an aluminum thin film refers to a thin film made of aluminum formed on the surface of a plastic substrate by a vacuum deposition method or the like. In particular, a plastic film with an aluminum thin film formed by laminating an aluminum thin film with a thickness of about several tens of nanometers on a plastic film is used as a member for a decorative film for in-mold molding or insert molding. In recent years, it has been applied to housings of various electronic products such as mobile phones, audio products, personal computers, automobile interior parts, and the like.

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

  For example, Patent Document 1 describes an undercoat agent containing a polyol having a predetermined glass transition temperature and a hydroxyl group equivalent, and a polyisocyanate, and it is said that adhesion between a plastic film and an aluminum thin film is improved.

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

  Therefore, the present applicant has proposed an undercoat agent through Patent Document 2 containing an acrylic copolymer having a predetermined hydroxyl group concentration, which is a reaction product of alkyl (meth) acrylates and hydroxyl group-containing (meth) acrylates, and polyisocyanate. According to this, not only the adhesion between the plastic film and the aluminum vapor deposition film becomes good, but even when the plastic film with the aluminum thin film is placed in a high temperature state, the aluminum thin film is hardly whitened.

JP 2009-227837 A JP 2011-132521 A

  On the other hand, when this inventor puts the plastic with an aluminum thin film according to Patent Document 2 under high temperature and high humidity, there are cases where a lot of minute transparent portions (hereinafter also referred to as “missing”) may occur on the surface of the aluminum thin film. I found it. Therefore, the present inventor does not deteriorate the adhesion between the aluminum thin film and the plastic substrate even when the plastic with the aluminum thin film is placed under high temperature and high humidity, and does not cause a whitened portion or a dropout on the aluminum thin film surface. Providing an undercoat agent was set as the main issue.

  The present inventor has made one hypothesis about “missing” that occurs when a plastic with an aluminum thin film obtained using the undercoat agent of Patent Document 2 is placed under high temperature and high humidity. That is, this part is formed of some reaction product of aluminum and water, and is transparent to visible light. As shown in FIG. 1, innumerable minute holes are formed in the aluminum thin film. I thought it would seem. Therefore, the idea was to add a substance that suppresses such a reaction between the aluminum layer and water.

  And, as a result of examining the means for maintaining adhesion and whitening resistance while eliminating the problem of omission, by adding a predetermined polymer to an undercoat agent containing a predetermined acrylic polyol and polyisocyanate, the problem described above The present inventors have found that an undercoat agent that can solve the above problems can be obtained and completed the present invention.

  That is, the present invention is a reaction product of a monomer group including alkyl (meth) acrylates (a1) and hydroxyalkyl (meth) acrylates (a2), having a glass transition temperature of 0 to 100 ° C. and a hydroxyl group equivalent. An acrylic copolymer (A) having a pH of 0.8 to 3.5 meq / g, an isocyanate composition (B) containing a reaction product of triisocyanates (b1) and diols (b2), and a hydroxyl group-containing acrylic silicone resin ( It is related with the undercoat agent for plastics with an aluminum thin film containing the polymer (C) which consists of c1) and / or a hydroxyl-containing fluororesin (c2).

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

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

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

  The undercoat agent of the present invention is a transparent composition and has excellent stability over time (pot life) at room temperature. In addition to being excellent in initial adhesion between the aluminum thin film and the plastic substrate, the adhesion between the aluminum thin film and the plastic substrate under high temperature and high humidity (hereinafter also referred to as moisture and heat resistant adhesion), the aluminum thin film surface Excellent whitening resistance and drop resistance.

  The plastic with an aluminum thin film according to the present invention (excluding a film-like plastic) is suitable for a housing of various electronic products such as bottles and caps, mobile phones, audio products, personal computers and automobile interior parts.

  Moreover, the plastic film with an aluminum thin film according to the present invention is suitable for, for example, a member of a decorative film for in-mold molding or insert molding, as well as a packaging material such as a gas barrier film, a transparent conductive sheet, a reflective film, a film capacitor, and It is also suitable as a member for a display label.

It is a microscope picture (400 time) of the vapor deposition surface of the aluminum vapor deposition PET film in which "missing" has arisen. 2 is a micrograph (400 times) of a vapor deposition surface of an aluminum vapor-deposited PET film according to Example 1. FIG.

  The undercoat agent of the present invention comprises a predetermined acrylic copolymer (A) (hereinafter also referred to as component (A)), an isocyanate composition (B) (hereinafter also referred to as component (B)), and a hydroxyl group-containing acrylic silicone. Polymer (C) (hereinafter also referred to as (C) component) comprising resin (c1) (hereinafter also referred to as (c1) component) and / or hydroxyl group-containing fluororesin (c2) (hereinafter also referred to as (c2) component). Is an essential component.

  The component (A) includes alkyl (meth) acrylates (a1) (hereinafter also referred to as (a1) component) and hydroxyalkyl (meth) acrylates (a2) (hereinafter also referred to as (a2) component). It is a reaction product (copolymer) of a monomer group.

  As the component (a1), various known alkyl (meth) acrylates can be used. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, (meth) acrylic Tert-butyl acid, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexadecyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, icosyl (meth) acrylate, ( Examples thereof include docosyl acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentanyl (meth) acrylate, and isobornyl (meth) acrylate, and these may be used alone or in combination. A combination of the above can be used. Among them, an alkyl (meth) acrylate having an alkyl group having about 1 to 20 carbon atoms, preferably about 1 to 8 is easy to make the glass transition temperature of the component (A) within the range described below, and the undercoat agent of the present invention. In particular, it is preferable because it contributes to the improvement of the drop resistance.

  The component (a2) is a monomer that gives the component (A) a hydroxyl group that becomes a reaction point with the component (B), and various known hydroxyalkyl (meth) acrylates can be used. Specifically, for example, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-methacrylic acid 3- Hydroxybutyl, 4-hydroxybutyl (meth) acrylate, hydroxycyclohexyl (meth) acrylate, 4- (hydroxymethyl) cyclohexylmethyl (meth) acrylate, 4- (hydroxymethyl) cyclohexylmethyl 2-hydroxypropionate, etc. Can be mentioned. Among these, those having about 1 to 4 carbon atoms of the hydroxyalkyl group are preferable from the viewpoint of the pot life of the undercoat agent of the present invention.

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

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

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

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

  Examples of the radical polymerization initiator include hydrogen peroxide, ammonium persulfate, potassium persulfate, t-butyl peroxybenzoate, dicumyl peroxide, lauryl peroxide, 2,2′-azobisisobutyronitrile and dimethyl- 2,2′-azobisisobutyrate and the like can be mentioned, and the amount used is usually in the range of about 0.1 to 2% by weight based on the total weight of the monomer group constituting the component (A).

  The component (A) thus obtained has a glass transition temperature of 0 to 100 ° C. and a hydroxyl group equivalent of 0.8 to 3.5 meq / g. And since such (A) component is well compatible with (B) component and (C) component, the undercoat agent of this invention becomes transparent, and long-term storage at room temperature is attained. In addition, by reacting such a component (A) and a component (C) described later with a component (B) described later, a crosslinked structure is introduced into the cured layer of the undercoat agent of the present invention. It is considered that the initial layer adhesion, wet heat resistance, whitening resistance and drop resistance of the layer are improved. From this viewpoint, the glass transition temperature of the component (A) is preferably about 25 to 80 ° C., and the hydroxyl group equivalent is preferably about 1 to 2.5 meq / g.

  In the case where α, β unsaturated carboxylic acids are used in combination with the component (a3), the carboxyl group equivalent of the component (A) is usually about 0.06 to 0.4 meq / g, preferably 0.09 to 0. .About 18 meq / g.

  In addition, the other physical properties of the component (A) are not particularly limited, but the weight average molecular weight is usually 3000 to 3000 from the viewpoint of initial adhesion, wet heat resistance, whitening resistance and slipping resistance of the undercoat agent of the present invention. About 100,000, preferably about 10,000 to 80,000.

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

  As the component (b1), triisocyanate as a multimer of various known diisocyanates is preferable. Examples of the diisocyanate include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and lysine diisocyanate, and dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1 , 4-cyclohexane diisocyanate, hydrogenated xylene diisocyanate and hydrogenated tolylene diisocyanate, and the like. Examples of multimers include nurate bodies and adduct bodies. Moreover, (b1) component can be used individually by 1 type or in combination of 2 or more types. Among these, aromatic diisocyanate multimers, particularly nurate bodies and / or adduct bodies are particularly preferred from the viewpoints of heat-and-moisture resistance, whitening resistance, and slip-out resistance.

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

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

  The component (B) thus obtained has an isocyanate group equivalent of 1 to 10 meq / g. Therefore, the compatibility, pot life, initial adhesion, wet heat and heat resistance, whitening resistance and resistance of the undercoat agent of the present invention. The slipperiness is improved. From this viewpoint, the corresponding amount is preferably about 3 to 6 meq / g.

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

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

  The component (C) is a polymer having a hydrophobic site (silicone chain, fluorine chain) and a hydroxyl group in the molecule, and as a result of forming a network structure by urethanation with the component (B) together with the component (A), It is considered that the wet heat and heat resistance and whitening resistance of the undercoat agent of the present invention are improved, and in particular, the anti-detachment property is improved based on the hydrophobic portion.

  As the component (c1), various known resins can be used without particular limitation as long as they are acrylic silicone resins having a hydroxyl group in the molecule. Specific examples include those obtained by grafting silicone chains to an acrylic resin. For example, JP 2003-192988 A, JP 2009-052019 A, JP 2009-24984 A, and JP 2010-228116 A. What was described in the gazette etc. can be used. The physical properties of the component (c1) are not particularly limited, but usually the hydroxyl value (mgKOH / g) is about 5 to 150. The weight average molecular weight is about 3000 to 100,000. Examples of the commercially available component (c1) include ZX-028-B manufactured by T & K TOKA.

  As the component (c2), various known resins can be used without particular limitation as long as they are fluorine-based resins having a hydroxyl group in the molecule. Specifically, for example, a fluoroolefin / vinyl ether copolymer having a hydroxyl group can be mentioned, which includes a fluoroolefin monomer (tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, perfluoropropyl vinyl ether, etc.) , Hydrocarbon monomers (vinyl ethers, vinyl carboxylates, allyl ethers, allyl carboxylates, isopropenyl ethers, etc.) and monomers having curing reactive sites such as hydroxybutyl vinyl ether and glycidyl vinyl ether It is a copolymer obtained by reaction. The physical properties of the fluoroolefin / vinyl ether copolymer are not particularly limited, but usually the hydroxyl value (mgKOH / g) is about 5 to 150. The weight average molecular weight is about 5000 to 50000. Moreover, a fluorine content rate is about 20-30 mass% normally. Examples of commercially available components (c2) include Lumiflon LF916F, Lumiflon LF200, Lumiflon LF400, Lumiflon LF710F, and Lumiflon LF810 manufactured by Asahi Glass Co., Ltd., ZX-022-H, ZX-007-C made by T & K TOKA, ZX-001 and ZX-022, BYK-SILCLEAN3700 manufactured by Big Chemie Japan Co., Ltd. and the like can be mentioned.

  Although the usage-amount of (C) component is not specifically limited, About 0.5-15 weight part is preferable with respect to a total of 100 weight part of (A) component and (B) component, Preferably it is about 2-10 weight part normally. is there. In such a range, the initial adhesiveness, wet heat resistant adhesiveness, whitening resistance and dropout resistance of the undercoat agent of the present invention are particularly good.

  The undercoat agent of the present invention can be obtained by mixing the component (A), the component (B) and the component (C) by various known methods. The undercoat agent is preferably used as a solution of an organic solvent (D) (hereinafter also referred to as component (D)), and its solid content weight is usually about 5 to 50% by weight.

  Examples of the component (D) include ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aromatic solvents such as toluene and xylene; and low solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol and butyl alcohol. Molecular alcohol solvents; glycol ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and propylene glycol monomethyl ether acetate; ethyl acetate, butyl acetate, methyl cellosolve acetate and cellosolve acetate Ester solvents such as Solvesso # 100 Fine Solvesso # 150 (trade name manufactured by Exxon Corporation..) Petroleum solvents and the like; other chloroform and dimethylformamide and the like. Among these, from the viewpoints of the dissolving power of the components (A) to (C) and the pot life of the undercoat agent of the present invention, the component (D) preferably contains a ketone solvent, particularly methyl ethyl ketone. Moreover, although the usage-amount of (D) component is not specifically limited, Usually, the solid content weight of the undercoat agent of this invention is the range used as about 10 to 50 weight%.

  In addition, the undercoat agent of the present invention includes other additives such as urethanization catalysts (tin-based, tertiary amine-based, etc.), Lewis acid catalysts, leveling agents, antioxidants, ultraviolet absorbers, The reaction solvent can be added as a diluent solvent.

  The plastic film with an aluminum thin film of the present invention is a composite film having various known plastic films, a layer comprising the undercoat agent of the present invention, and an aluminum thin film layer. Specifically, after forming the undercoat layer by applying the coating agent of the present invention to the plastic film by various known means and usually heat-curing at about 80 to 185 ° C. for about 10 seconds to 5 minutes. It can be obtained by further laminating an aluminum species on the undercoat layer by various known thin film forming methods.

  Examples of the plastic film include polyester film, polyvinyl chloride film, polyamide film, polyimide film, polycarbonate film, polyethylene film, and polypropylene film.

Examples of the coating means 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 dry solid content.

  Examples of the thin film forming method include various physical methods (vacuum thermal vapor deposition, sputtering, etc.) and chemical methods (chemical vapor phase reaction, etc.). The thickness of the aluminum thin film is not particularly limited, but is usually about 5 to 500 nm, preferably about 5 to 50 nm.

  The plastic film with an aluminum thin film of the present invention may be provided with other functional layers depending on the application. For example, when the film is used for in-mold molding transfer foil, a release layer, a hard coat layer, an anchor layer for a hard coat layer, a pattern ink layer, and the like may be provided between the plastic film layer and the undercoat layer. it can. An adhesive layer can also be provided on the aluminum thin film layer.

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

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

<Preparation of component (A)>
Production Example 1
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, 192 parts (1.92 mol) of methyl methacrylate and 7.2 parts of normal butyl acrylate (0) as component (a1) 0.06 mol), 40.8 parts (0.35 mol) of 2-hydroxyethyl acrylate, and 360 parts of methyl ethyl ketone were charged, and the reaction system was set to 80 ° C. Next, 1.2 parts of azobisisobutyronitrile was charged, and the temperature was kept at around 80 ° C. for 5 hours. Next, 2.4 parts of azobisisobutyronitrile was charged, and the reaction system was further kept at the same temperature for 4 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution (non-volatile content 30%) of an acrylic copolymer (A-1) having a glass transition temperature of 70 ° C., a hydroxyl group equivalent of 1.42 meq / g, and a weight average molecular weight of 50000.

Production Example 2
A reaction vessel similar to Production Example 1 was charged with 189.6 parts of methyl methacrylate, 4.8 parts of normal butyl acrylate, 45.6 parts of 2-hydroxyethyl methacrylate, and 360.0 parts of methyl ethyl ketone. Was set to 80 ° C. Next, 1.2 parts of azobisisobutyronitrile was charged, and the temperature was kept at around 80 ° C. for 5 hours. Next, 2.4 parts of azobisisobutyronitrile was charged, and the reaction system was further kept at the same temperature for 4 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution (30% nonvolatile content) of an acrylic copolymer (A-2) having a glass transition temperature of 90 ° C., a hydroxyl group equivalent of 1.42 meq / g, and a weight average molecular weight of 50000.

Production Example 3
A reaction vessel similar to Production Example 1 was charged with 117.6 parts of methyl methacrylate, 81.6 parts of normal butyl acrylate, 40.8 parts of 2-hydroxyethyl acrylate, and 360.0 parts of methyl ethyl ketone. Was set to 80 ° C. Next, 1.2 parts of azobisisobutyronitrile was charged, and the temperature was kept at around 80 ° C. for 5 hours. Next, 2.4 parts of azobisisobutyronitrile was charged, and the reaction system was further kept at the same temperature for 4 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution (30% nonvolatile content) of an acrylic copolymer (A-3) having a glass transition temperature of 10 ° C., a hydroxyl group equivalent of 1.42 meq / g, and a weight average molecular weight of 55000.

Production Example 4
In a reaction vessel similar to Production Example 1, 194.4 parts of methyl methacrylate, 14.4 parts of normal butyl acrylate, 31.2 parts of 2-hydroxyethyl acrylate, and 360.0 parts of methyl ethyl ketone were charged. Was set to 80 ° C. Next, 1.2 parts of azobisisobutyronitrile was charged, and the temperature was kept at around 80 ° C. for 5 hours. Next, 2.4 parts of azobisisobutyronitrile was charged, and the reaction system was further kept at the same temperature for 4 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution (non-volatile content 30%) of an acrylic copolymer (A-4) having a glass transition temperature of 70 ° C., a hydroxyl group equivalent of 1.07 meq / g, and a weight average molecular weight of 50,000.

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

Production Example 6
In the same reaction vessel as in Production Example 1, 70.8 parts of methyl methacrylate, 84.0 parts of normal butyl acrylate, 64.8 parts of 2-hydroxyethyl acrylate, 20.4 parts of styrene, and 360.0 methyl ethyl ketone The reaction system was set to 80 ° C. Next, 1.2 parts of azobisisobutyronitrile was charged, and the temperature was kept at around 80 ° C. for 5 hours. Next, 2.4 parts of azobisisobutyronitrile was charged, and the reaction system was further kept at the same temperature for 4 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution (30% nonvolatile content) of an acrylic copolymer (A-6) having a glass transition temperature of 0 ° C., a hydroxyl group equivalent of 2.31 meq / g, and a weight average molecular weight of 55000.

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

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

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

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

Comparative production example 1
In the same reaction vessel as in Production Example 1, 177.6 parts of methyl methacrylate, 20.9 parts of normal butyl acrylate, 17.5 parts of 2-hydroxyethyl acrylate, 24.0 parts of styrene, and 360.0 methyl ethyl ketone The reaction system was set to 80 ° C. Next, 1.2 parts of azobisisobutyronitrile was charged, and the temperature was kept at around 80 ° C. for 5 hours. Next, 2.4 parts of azobisisobutyronitrile was charged, and the reaction system was further kept at the same temperature for 4 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution (non-volatile content 30%) of an acrylic copolymer (A) having a glass transition temperature of 70 ° C., a hydroxyl group equivalent of 0.62 meq / g, and a weight average molecular weight of 45,000.

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

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

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

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

<Preparation of component (B)>
Production Example 2
445.5 parts of coronate 2030, 5.0 parts of 1,6-hexanediol and 308.6 parts of methyl ethyl ketone were charged in the same reaction vessel as in Production Example 1, and the urethanization reaction was carried out at 60 ° C. for 3 hours. Thereafter, the mixture was cooled to room temperature to obtain a modified tolylene diisocyanurate having an isocyanate group equivalent of 1 meq / g (hereinafter referred to as “modified TDI”).

<Preparation of undercoat agent>

Example 1
(A-1) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), (c1) Hydroxyl group-containing acrylic silicone resin (product name “ZX-028-G”) ”, 0.6 part by T & K TOKA, hydroxyl value 115 mgKOH / g), and 10.6 parts of methyl ethyl ketone were mixed well to prepare an undercoat agent.

Example 2
(A-2) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), ZX-028-G 0.6 part, and methyl ethyl ketone 10.6 parts are mixed well. And an undercoat agent was prepared.

Example 3
(A-3) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), ZX-028-G 0.6 part, and methyl ethyl ketone 10.6 parts are mixed well. And an undercoat agent was prepared.

Example 4
(A-4) Component 10.0 parts, (B-1) Component 6.5 parts (NCO / OH = 2.0), ZX-028-G 0.6 part, and methyl ethyl ketone 10.2 parts are mixed well. And an undercoat agent was prepared.

Example 5
(A-5) Component 10.0 parts, (B-1) Component 6.5 parts (NCO / OH = 2.0), ZX-028-G 0.6 part, and methyl ethyl ketone 10.2 parts are mixed well. And an undercoat agent was prepared.

Example 6
(A-6) Component 10.0 parts, (B-1) Component 14.0 parts (NCO / OH = 2.0), ZX-028-G 0.6 parts, and methyl ethyl ketone 14.8 parts are mixed well. And an undercoat agent was prepared.

Example 7
(A-7) Component 10.0 parts, (B-1) Component 6.5 parts (NCO / OH = 2.0), ZX-028-G 0.6 part, and methyl ethyl ketone 10.2 parts are mixed well. And an undercoat agent was prepared.

Example 8
(A-8) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), ZX-028-G 0.6 part, and methyl ethyl ketone 10.6 parts are mixed well. And an undercoat agent was prepared.

Example 9
(A-9) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), ZX-028-G 0.6 part, and methyl ethyl ketone 10.6 parts are mixed well. And an undercoat agent was prepared.

Example 10
(A-10) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), ZX-028-G 0.6 part, and methyl ethyl ketone 10.6 parts are mixed well. And an undercoat agent was prepared.

Example 11
(A-1) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), (c1) Hydroxyl group-containing acrylic silicone resin (product name “BYK-SILCLEAN3700”, An undercoat agent was prepared by thoroughly mixing 1.0 part of a hydroxyl value 30 mg KOH / g) manufactured by Big Chemie Japan Co., Ltd. and 10.2 parts of methyl ethyl ketone.

Example 12
(A-1) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), BYK-SILCLEAN3700 0.5 part, and methyl ethyl ketone 10.6 parts are mixed well. An undercoat agent was prepared.

Example 13
(A-1) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), (c2) Fluoroethylene-vinyl ether copolymer containing a hydroxyl group as a component (product name) “Lumiflon LF916F”, manufactured by Asahi Glass Co., Ltd., 0.3 part of hydroxyl value 98 mgKOH / g, fluorine content 25.6% by mass) and 10.3 parts of methyl ethyl ketone were mixed well to prepare an undercoat agent.

Example 14
(A-1) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), Lumiflon LF916F 0.15 part, and methyl ethyl ketone 10.1 parts are mixed well, A coating agent was prepared.

Example 15
(A-1) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), ZX-028-G 0.3 part, and methyl ethyl ketone 10.2 parts are mixed well. And an undercoat agent was prepared.

Example 16
(A-1) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), ZX-028-G 0.9 part, and methyl ethyl ketone 11.0 parts are mixed well. And an undercoat agent was prepared.

Example 17
(A-1) Component 10.0 parts, (B-1) Component 4.3 parts (NCO / OH = 1.0), ZX-028-G 0.46 parts, and methyl ethyl ketone 9.3 parts are mixed well. And an undercoat agent was prepared.

Example 18
(A-1) Component 10.0 parts, (B-1) Component 12.8 parts (NCO / OH = 3.0), ZX-028-G 0.73 parts, and methyl ethyl ketone 10.8 parts are mixed well. And an undercoat agent was prepared.

Example 19
(A-1) Component 10.0 parts, (B-2) Component 6.5 parts (NCO / OH = 2.0), ZX-028-G 0.6 part, and methyl ethyl ketone 10.6 parts are mixed well. And an undercoat agent was prepared.

Comparative Example 1
An undercoat agent was prepared by thoroughly mixing 10 parts of the component (A-1) of Production Example 1 and 8.6 parts of the component (B-1).

Comparative Example 2
An undercoat agent was prepared by thoroughly mixing 10 parts of component (a), 3.8 parts of component (B-1), 0.44 parts of ZX-028-G, and 8.6 parts of methyl ethyl ketone. .

Comparative Example 3
(B) Component 10.0 parts, (B-1) Component 10.7 parts (NCO / OH = 2.0), ZX-028-G 0.67 parts, and methyl ethyl ketone 11.0 parts were mixed well. An undercoat agent was prepared.

Comparative Example 4
An undercoat agent was prepared by thoroughly mixing 10 parts of component (A), 3.8 parts of component (B-1), 0.22 part of Lumiflon LF916F, and 8.4 parts of methyl ethyl ketone.

Comparative Example 5
(B) Component 10.0 parts, (B-1) Component 10.7 parts (NCO / OH = 2.0), Lumiflon LF916F 0.33 parts, and methyl ethyl ketone 10.8 parts are mixed well, and undercoat An agent was prepared.

Comparative Example 6
(A-1) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), (c1) In place of component, polyester-modified hydroxyl group-containing polydimethylsiloxane (product name “BYK”) -370 ", manufactured by Big Chemie Japan Co., Ltd., 0.5 parts of hydroxyl value 35 mgKOH / g) and 10.6 parts of methyl ethyl ketone were mixed well to prepare an undercoat agent.

Comparative Example 7
(A-1) Component 10.0 parts, (B-1) Component 8.6 parts (NCO / OH = 2.0), (c1) Instead of component 3-isocyanatopropyltriethoxysilane (trade name “KBE”) -9007 "(Shin-Etsu Chemical Co., Ltd.) 0.56 part and 11.5 parts of methyl ethyl ketone were mixed well to prepare an undercoat agent.

<Preparation of test panel>
A commercially available hard coat agent (trade name “Aronix M305”, manufactured by Toa Gosei Co., Ltd.) is applied to a polyethylene terephthalate film that has been subjected to a release treatment so that the film thickness after drying and curing is 5 μm on a bar coater. And cured at an illuminance of 100 mj / cm ² . Next, the undercoat agent according to Example 1 was applied on the hard coat layer with a bar coater so that the dry film thickness was 1 μm. Next, the obtained coated film was cured with a circulating dryer (150 ° C., 60 seconds). Next, a commercially available vapor deposition apparatus (product name “NS-1875-Z”, manufactured by Nishiyama Seisakusho Co., Ltd.) was used for the coating film to obtain an aluminum vapor deposition film having a vapor deposition layer thickness of 50 nm. Next, an adhesive was coated on the aluminum vapor deposition layer with a bar coater so that the dry film thickness was 1 μm. Next, the obtained coated film was dried with a circulating dryer (80 ° C., 10 seconds). This was thermally transferred to a commercially available acrylic plate and used as a test panel of Example 1. Test panels were similarly prepared for the undercoat agents of other examples and comparative examples.

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

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

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

(Whitening resistance)
The whitening state after each test panel was placed under constant temperature and humidity conditions of 65 ° C. and 95% × 24 hours was visually evaluated according to the following criteria.
5 ... Whitening is not generated on the aluminum surface and the metallic luster is maintained. 4 ... Whitening is slightly generated on the aluminum surface, but the metallic luster is almost maintained. 3 ... The entire aluminum surface. There is slight whitening, and some loss of metallic luster is observed 2 ... Whitening is strongly occurring on the entire aluminum surface, and disappearance of metallic luster is observed 1 ... Whitening is more intense on the entire aluminum surface Has occurred and the metallic luster has completely disappeared

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

5 ... No omission in the aluminum layer 4 ... Some omissions occur locally on the aluminum surface 3 ... Occasional omissions occur slightly on the entire aluminum surface 2 ... Many omissions occur on the entire aluminum surface ing.
1 ... Many large omissions occur on the entire aluminum surface.

Claims (11)

A reaction product of a monomer group including alkyl (meth) acrylates (a1) and hydroxyalkyl (meth) acrylates (a2), having a glass transition temperature of 0 to 100 ° C. and a hydroxyl group equivalent of 0.8 to An acrylic copolymer (A) of 3.5 meq / g;
An isocyanate composition (B) containing a reaction product of triisocyanates (b1) and diols (b2) and having an isocyanate group equivalent of 1 to 10 meq / g;
A polymer (C) comprising a hydroxyl group-containing acrylic silicone resin (c1) and / or a hydroxyl group-containing fluororesin (c2);
Containing
Undercoat agent for plastic with aluminum thin film. The undercoat agent of Claim 1 whose carbon number of the alkyl group of (a1) component is 1-20. The undercoat agent according to claim 1 or 2, wherein the hydroxyalkyl group of the component (a2) has 1 to 4 carbon atoms. The undercoat agent according to any one of claims 1 to 3, wherein the component (b1) is an aromatic diisocyanate trimer and the component (b2) is an alkylene diol having 2 to 8 carbon atoms. The undercoat agent according to any one of claims 1 to 4, wherein a ratio [NCO / OH] of the hydroxyl group equivalent of the component (A) and the isocyanate group equivalent of the component (B) is 1 to 6. The amount of the component (C) used is in the range of 0.5 to 15 parts by weight with respect to 100 parts by weight of the sum of the components (A) and (B). Coating agent. The undercoat agent according to any one of claims 1 to 6, which is used as a solution of an organic solvent (D). A plastic with an aluminum thin film, comprising a plastic substrate (excluding a plastic film), a layer comprising the undercoat agent according to any one of claims 1 to 7, and an aluminum thin film layer. The plastic film with an aluminum thin film which has a plastic film, the layer which consists of an undercoat agent in any one of Claims 1-7, and an aluminum thin film layer. A decorative film for in-mold molding, comprising the plastic film with an aluminum thin film according to claim 9 as a member. A decorative film for insert molding, comprising the plastic film with an aluminum thin film according to claim 9 as a member.