JP2013216745A - Ultraviolet-curing type undercoating agent for deposition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the adhesiveness between a metal-deposited layer and an ultraviolet-curing type undercoat layer, and to make the appearance in orange peel shape better.SOLUTION: An ultraviolet-curing type undercoating agent for deposition contains (a) a mixture of (a1) a polyfunctional (meth)acrylate having a (meth)acryloyl group and (a2) an acrylic polyol, (b) a silicone-based surface regulator, (c) a photopolymerization initiator, and (d) an organic solvent as essential components, wherein the weight ratio of the component (a1) to the component (a2) is from 30:70 to 70:30, and the solid component ratio of the component (b) to the component (a) is from 100:0.01 to :0.5.

Description

  The present invention relates to an ultraviolet curable undercoat agent for vapor deposition.

  Conventionally, ultraviolet curable resin compositions are widely used in fields such as adhesives and paints because they are cured by short-time ultraviolet irradiation.

In the technical field related to the present invention, metal vapor deposition coating is known as a method for imparting a radiant sensation peculiar to metals such as aluminum, gold, silver and platinum to the surface of plastics such as polypropylene and polycarbonate. As shown in FIG. 2, the layer structure is composed of a plastic substrate such as an acrylic plate, an ABS plate, and a polycarbonate plate, an ultraviolet curable undercoat layer, a metal vapor-deposited layer, an ultraviolet curable hard coat layer, and the like. The primer layer) is indispensable for strengthening the adhesion between the plastic substrate and the metal deposition layer.
JP 2002-285083 A JP 2006-169212 A JP 2010-202877 A

  However, there is a problem that the appearance is deteriorated if the adhesion is secured by using the conventional UV curable anchor coating agent, and the adhesion is deteriorated if the appearance is maintained.

  The present invention has been studied for the purpose of eliminating the skin-like appearance while maintaining the adhesion between the metal vapor-deposited layer and the ultraviolet curable undercoat layer, and (a) (a1) (meth) acryloyl A mixture of a polyfunctional (meth) acrylate having a group and (a2) acrylic polyol, (b) a silicone-based surface conditioner, (c) a photopolymerization initiator, and (d) an organic solvent as essential components, The weight ratio of the component (a1) and the component (a2) is 30:70 to 70:30, and the component (b) is 100: 0.01 to 0 in a solid content ratio with respect to the component (a). The above-mentioned problem can be solved by using an ultraviolet curable undercoat agent for vapor deposition, which is .5.

  By using the UV curable vapor deposition undercoat agent, the appearance and adhesion are excellent. The present invention will be described in detail.

  In the present invention, a mixture of (a) (a1) (meth) acryloyl group-containing polyfunctional (meth) acrylate and (a2) acrylic polyol is used, and the blending ratio is preferably 30:70 to 70:30 in the former: latter. If it deviates from this range, as shown in Comparative Examples 1 to 4, the appearance tends to be distorted and the adhesion tends to be poor.

  As the polyfunctional (meth) acrylate having a (meth) acryloyl group, those having at least three (meth) acryloyl groups in the molecule are preferably used because they express the hardness and toughness of the coating film. For example, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, trimethylolpropane tetra (meth) acrylate, tris (acryloxyethyl) Isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( Acrylate), dipentaerythritol hexa (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipenta Examples include erythritol hexa (meth) acrylate and mixtures of two or more thereof.

  Among the polyfunctional (meth) acrylates, dipentaerythritol hexaacrylate (DPHA), dipentaerythritol pentaacrylate (DPPA), or a mixture thereof is particularly preferable from the viewpoint of coating strength.

  The acrylic polyol is a non-reactive acrylic polymer obtained by copolymerizing at least a hydroxyl group-containing monomer and a copolymerizable monomer with a known polymerization method, for example, solution polymerization. Contributes to flexibility and adhesion to substrates and metal deposition films. Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, and 4-hydroxybutyl acrylate.

  Examples of monomers copolymerizable with a hydroxyl group-containing monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isononyl acrylate, lauryl acrylate, and stearyl acrylate. Acrylic acid alkyl ester monomers, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate and other methacrylic acid alkyl ester monomers, styrene, α-methylstyrene, vinyl toluene, ethyl vinyl benzene Aromatic vinyl monomers such as vinyl acetate, vinyl propionate, vinyl saturated fatty acid such as vinyl propionic acid, acrylonitrile, meta Vinyl cyanide monomers such as rilonitrile, olefin monomers such as ethylene, propylene and butadiene, ethylene carboxylic acids such as methacrylic acid, crotonic acid, citraconic acid, itaconic acid, maleic acid and fumaric acid, maleic anhydride Ethylene carboxylic anhydrides such as acids, monoalkyl esters of ethylene dicarboxylic acids such as monobutyl maleic acid, and ethylene carboxylates such as ammonium salts or alkali metal salts thereof, acrylamide, methacrylamide, diacetone acrylamide Such as ethylene carboxylic acid amides, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and other ethylene carboxylic acid esters with amino group-containing alcohols alone or in combination of two or more. They can be used together.

  (B) Examples of the silicone surface conditioner include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, polyester-modified methylalkylsilokine san, and polyether-modified polymethylalkylsiloxane. The group-containing polyester-modified polydimethylsiloxane becomes a part of the coating film and does not inhibit the adhesion. Examples of commercially available products include BYK-UV3570 (trade name, BYK is a registered trademark, manufactured by Big Chemie Japan). Component (b) is preferably blended in an amount of 0.01 to 0.5 parts by weight, more preferably 0.05 to 0.1 parts by weight, based on 100 parts by weight of the solid content of component (a), and the lower limit is not reached. When the upper limit is exceeded, the adhesion with the metal vapor deposition layer tends to be poor.

  In addition to the above components, a compound capable of generating radicals by ultraviolet rays, electron beams, radiation, etc., so-called (c) photopolymerization initiator, is blended in order to cure by irradiating ultraviolet rays. Examples of the photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2 -Propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino Acetophenones such as phenyl) butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether Etc. Zoins, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2 , 4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride Benzophenones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) Thioxanthones such as 3,4-dimethyl -9H- thioxanthone-9-Onmesokurorido, and the like.

  Commercially available photopolymerization initiators include IRGACURE 184, 369, 651, 500, 907, CGI 1700, CGI 1750, CGI 1850, CG 24-61, Lucirin LR8728, Darocure 1116, 1173 (above, BASF Japan Ltd., trade name), Uvekril P36 ( UCB, product name) and the like.

  (C) The blending ratio of the photopolymerization initiator is 0.3 to 15 parts by weight, more preferably 0.5 to 7 parts by weight based on 100 parts by weight of the solid content of the component (a). If it is in this range, the undercoat agent for ultraviolet curable vapor deposition of the present invention can be cured well. If the lower limit is not reached, the crosslink density is lowered and the adhesion to the metal vapor deposition layer and the plastic layer tends to be inferior. If the upper limit is exceeded, it is excessively cured and the adhesion tends to be inferior, and cracks are likely to occur.

  Specific examples of the organic solvent (d) used for viscosity adjustment include aromatic hydrocarbons such as toluene and xylene, aliphatic esters such as ethyl acetate, butyl acetate and isobutyl acetate, cyclohexane and the like. Alicyclic hydrocarbons, aliphatic hydrocarbons such as hexane and pentane, aliphatic ketones such as methyl ethyl ketone and methyl isobutyl ketone, alcohols such as isopropanol and 1-butanol, etc. are particularly limited. It is not a thing. These solvents may be used alone or in combination of two or more. In addition, the usage-amount of a solvent is not specifically limited.

  In addition, in order to suppress the generation of oxygen radicals that can be generated by light energy and prevent deterioration due to light, (e) a light stabilizer may be added, for example, bis (2,2,6,6, -tetra Methyl-4-piperidyl) sebacate, bis (1,2,2,6,6, -pentamethyl-4-piperidyl) sebacate, 1- [2- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6, -tetramethylpiperidine, 4-benzoyl Hindered amine light stabilizers (HALS) such as oxy-2,2,6,6, -tetramethylpiperidine, ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl- Cyanoacrylate light stabilizers such as cyano-3,3′-diphenyl acrylate and butyl 2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, 2,4-di-t-butylphenyl-3 Benzoate-based light stabilizers such as 1,5-di-t-butyl-4-hydroxybenzoate, and hindered amine-based light stabilizers (HALS) which have a greater effect in a small amount are particularly preferable.

  The blending ratio of the light stabilizer is preferably 0.05 to 5 parts by weight based on 100 parts by weight of the solid content of the component (a), and if within this range, it depends on the light of the resin composition according to the present invention. It can prevent deterioration and can be cured well. If the lower limit is not reached, deterioration due to light tends to be caused. If the upper limit is exceeded, the curability of the UV curable vapor deposition undercoat agent may be lowered, and insoluble matter may be caused.

  The undercoat agent for ultraviolet curable vapor deposition of this invention is apply | coated to a base material by spray coating, brush coating, etc. so that the film thickness after hardening may be 5-30 micrometers. Examples of ultraviolet lamps that irradiate ultraviolet rays include low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, xenon lamps, gallium lamps, and metal halide lamps. Irradiation may be performed in an inert gas such as nitrogen or argon. Hereinafter, examples, reference examples, and comparative examples will be described in detail.

(A) component (a1) 50 parts by weight of dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA, Nippon Kayaku Co., Ltd., solid content 100%), (a2) MMA (methyl methacrylate) and 2-HEMA ( A blend of 50 parts by weight of a 2-hydroxyethyl methacrylate copolymer (weight average molecular weight of about 7600, OH value of 27 mg · KOH) was used.

(D) Component As component (d), an organic compound containing 3 parts by weight of ethyl acetate, 5 parts by weight of isobutyl alcohol, 44 parts by weight of toluene, 36 parts by weight of n-butanol, 9 parts by weight of butyl acetate, and 3 parts by weight of diacetone alcohol. Solvent was used.

UV-curing type undercoat agent for vapor deposition (a) 100 parts by weight of component, (b1) (b1) acrylic group-containing polyester-modified polydimethylsiloxane (BYK-UV3570) 0.05 part by weight, (c) 1 as component -1 part by weight of hydroxycyclohexyl phenyl ketone (IRGACURE184, manufactured by BASF Japan Ltd., trade name), 100 parts by weight of component (d), and hindered amine light stabilizer (TINUVIN152, BASF Japan Co., Ltd.) as component (e) An undercoat agent for ultraviolet curable vapor deposition was obtained by blending 0.8 part by weight of a product manufactured by company.

  In Example 1, it implemented similarly except having made the compounding quantity of (b1) into 0.075 weight part.

  In Example 1, it implemented similarly except having made the compounding quantity of (b1) into 0.1 weight part.

  In Example 2, it implemented similarly except having made (a1) 30 weight part and (a2) 70 weight part.

  In Example 2, it carried out similarly except having made (a1) 70 weight part and (a2) 30 weight part.

Reference example 1
In Example 1, it implemented similarly except having used (b2) acrylic group containing polyether modified polydimethylsiloxane (BYK-UV3500) instead of BYK-UV3570 as (b) component.

Reference example 2
In Example 3, it implemented similarly except having used (b6) polyester modified polydimethylsiloxane (BYK-310) instead of BYK-UV3570 as (b) component.

Reference example 3
In Example 1, the same procedure was used except that (b3) polysiloxane modified with polyether (Tego Glide 410, trade name, manufactured by Evonik Degussa Japan Co., Ltd.) was used as the component (b) instead of BYK-UV3570. Carried out.

Comparative Example 1
In Example 3, it carried out similarly except having (a1) 20 weight part and (a2) 80 weight part.

Comparative Example 2
In Example 2, it carried out similarly except having made (a1) 80 weight part and (a2) 20 weight part.

Comparative Example 3
In Example 2, the same procedure was carried out except that only (a1) dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA, Nippon Kayaku Co., Ltd., 100% solids) was used as component (a). did.

Comparative Example 4
In Example 2, as component (a) (a2) copolymer of MMA (methyl methacrylate) and 2-HEMA (2-hydroxyethyl methacrylate) (weight average molecular weight of about 7600, OH value of 27 mg · KOH) only 100 parts by weight It implemented similarly except having used.

Comparative Example 5
In Example 3, it carried out similarly except having used the acrylic polymer (Polyflow KL-700, a brand name, Kyoeisha Chemical Co., Ltd.) of the silicone side chain instead of BYK-UV3570 as (b) component.

The blending ratio and evaluation results are shown in Tables 1 and 2.

The evaluation results were as follows.
Preparation of test body It apply | coats with a spray so that the film thickness after hardening may be set to 10 micrometers on a PC (polycarbonate) board (1600, 5 cm x 10 cm x 2 mm thickness made by Takiron), and it dries at 80 degreeC for 5 minutes, and a solvent is used. It was volatilized and irradiated with ultraviolet rays under conditions of 100 mW / cm ² and 800 mJ / cm ² using an electroded high-pressure mercury lamp (manufactured by Eye Graphics).
Subsequently, metal aluminum is vapor-deposited thereon using a vacuum vapor deposition apparatus (manufactured by ULVAC), and further, an Aika Eyetron Z-774 (Aika Industry Co., Ltd., UV curable hard coat resin) is used as a hard coat layer thereon. , Solid content 50%) is spray-coated so that the film thickness after curing is 8 μm, dried at 80 ° C. for 5 minutes, and 100 mW / cm ² , 800 mJ using an electroded high-pressure mercury lamp (manufactured by Eye Graphics). UV irradiation was performed under the conditions of / cm ² .

Yuzu skin; Visually check the coated surface of the test specimen, ○ if there is no yuzu skin feeling, △ if there is a slight yuzu skin feeling, x if the yuzu skin feeling is clear and has no commercial value did.
Glossiness: The coated surface of the test specimen was visually confirmed. The glossiness was evaluated as “◯”, the glossiness was slightly inferior as “Δ”, and the glossiness and no commercial value was rated as “X”.
Adhesiveness: Based on a cross-cut test based on JIS K 5600-5-6 (1999 edition), 100 squares of 1 mm ² were prepared on the coating surface, and cellophane tape (product name CT-24, manufactured by Nichiban Co., Ltd.) And pull upwards to check the peeling condition. The number of squares that did not peel off was recorded, and the evaluation criteria were 100/100 as ◯, 50/100 to 99/100 as Δ, and 0 to 49/100 as x.
Frame: In the coating film formed on each base material, the width between the boundary surface generated in the coating film and the edge of the base material is measured, ○ within 2 mm width, Δ from 2 to 5 mm, Δ from 5 mm or more It was.

  The undercoating agent for ultraviolet curable vapor deposition of the present invention is a product to be subjected to metal vapor deposition coating, for example, electronic devices such as mobile phones, digital cameras, personal computers, audio players, game machines, cosmetic containers, grills, automobile emblems. And the adhesiveness between the substrate and the metal vapor deposition layer is excellent.

The structure sectional drawing of the coating film using the anchor coating agent for ultraviolet curable vapor deposition of this invention. Sectional drawing of the structure of the coating film using the conventional anchor coating agent for ultraviolet curable vapor deposition.

DESCRIPTION OF SYMBOLS 1 Plastic base material layer 3 Anchor coat layer 3 'Conventional anchor coat layer 5 Metal vapor deposition layer 8 Hard coat layer

Claims (3)

(A) (a1) a mixture of a polyfunctional (meth) acrylate having a (meth) acryloyl group and (a2) an acrylic polyol, (b) a silicone-based surface conditioner, (c) a photopolymerization initiator, (d ) An organic solvent is included as an essential component, the weight ratio of the component (a1) and the component (a2) is 30:70 to 70:30, and the component (b) is solid with respect to the component (a) An undercoat agent for ultraviolet curable vapor deposition, wherein the fraction ratio is 100: 0.01 to 0.5. The undercoat agent for ultraviolet curable vapor deposition according to claim 1, wherein the (b) silicone-based surface conditioner is an acrylic group-containing polyester-modified polydimethylsiloxane. The undercoat agent for ultraviolet curable vapor deposition according to claim 1 or 2, wherein the component (a1) is dipentaerythritol hexaacrylate.

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