WO2012017552A1 - Paint for metallized film and laminated body - Google Patents

Abstract

This paint for metallized film contains: (a) 10 to 40 mass % of a vinyl ester resin or an unsaturated polyester resin, (b) 30 to 60 mass % of a compound having a cyclic structure and one ethylenically-unsaturated group, (c) 5 to 40 mass % of a modifying agent (where the total of the aforementioned components (a) to (c) is 100 mass %), and (d) 0.1 to 15 parts by mass with respect to a total of 100 parts by mass of the aforementioned components (a) to (c) of an initiator.

Description

Paint for metal vapor deposition film and laminate

The present invention relates to paints and laminates for metal vapor deposited films, and in particular, soft and hard vinyl chloride resins; polystyrene; polycarbonate; glass; aluminum; steel plates; polyolefin resins or olefins modified with polar group-containing compounds and polar group-containing compounds. Magnesium; Acrylonitrile-butadiene-styrene copolymer; Acrylonitrile-styrene copolymer; Polyester resin; Adhesiveness to the layer of acrylic resin and adhesion to the metal vapor deposition film The present invention relates to a coating for a metal vapor deposition film having a good balance of moisture resistance, scratch resistance, paintability, decorating properties, transparency, surface smoothness, flexibility and impact resistance, and a laminate using the coating.

From the viewpoints of productivity and energy saving, UV curable resin compositions are widely used, and in particular, are used for hard coat processing on plastic molded products. Examples of applications in which the ultraviolet curable resin composition is used include, for example, reflectors such as lighting and lights, reflector parts, home appliances such as mobile phones, and decorative applications for cosmetic containers.

As a conventionally used ultraviolet curable resin composition, for example, Patent Document 1 discloses that the surface of a resin molded article is coated with excellent scratch resistance, weather resistance, and flexibility, and adhesion to the resin molded article. An ultraviolet curable resin composition for coating that gives a cured film excellent in the above has been proposed. However, when it is laminated on the surface of a resin molded product whose surface is coated with a metal, there is a problem that adhesion to the metal is not sufficient.

Further, in order to improve the adhesion to metal, for example, Patent Document 2 proposes an ultraviolet curable topcoat composition. However, in this case, the scratch resistance of the cured film is not sufficient.

JP 2000-281935 A JP 2007-314677 A

The object of the present invention is to provide various adherends, in particular, soft and hard vinyl chloride resins; polystyrene; polycarbonate; glass; aluminum; steel plates; polyolefin resins modified with polar group-containing compounds or olefins and polar group-containing compounds. Polymer; Magnesium; Acrylonitrile-butadiene-styrene copolymer; Acrylonitrile-styrene copolymer; Polyester resin; or Adhesion with a layer of acrylic resin; Adhesion with metal vapor deposition film; An object of the present invention is to provide a coating for a metal vapor deposition film having an excellent balance of scratch resistance, paintability, decorating properties, transparency, surface smoothness, flexibility and impact resistance, and a laminate using the coating.

As a result of diligent research, the present inventor has found that a paint containing the following components (a), (b), (c) and (d) in a specific quantitative relationship can solve the above problems. The present invention has been completed.

That is, the present invention is as follows.
1. (A) Vinyl ester resin or unsaturated polyester resin 10 to 40% by mass
(B) Compound having a cyclic structure and one ethylenically unsaturated group 30 to 60% by mass
(C) modifying agent 5-40% by mass,
(However, the total of the components (a) to (c) is 100% by mass)
And (d) Initiator A coating for a metal vapor-deposited film comprising 0.1 to 15 parts by mass with respect to a total of 100 parts by mass of the components (a) to (c).
2. 2. The metal vapor deposited film paint according to 1, wherein the component (a) is urethane (meth) acrylate.
3. 3. The coating for a metal vapor deposition film according to 1 or 2, wherein the component (b) is a monomer having an N-vinyl group.
4). The component (c) is a polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g; and a polyol (c-2) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g Modified rubber (c-3); at least one selected from the group consisting of compound (c-4) having an epoxy equivalent of 150 to 700 g / mol; The coating for metal vapor deposition films of description.
5. The component (c-1) is a castor oil-based polyol (c-1-1) having a hydroxyl value of 40 to 330 mgKOH / g; a polybutadiene-based polyol (c-1-2) having a hydroxyl value of 40 to 330 mgKOH / g; 5. The metal-deposited film coating material according to 4 above, which is at least one selected from the group consisting of a polyisoprene-based polyol having a value of 40 to 330 mg KOH / g or a hydrogenated product (c-1-3) thereof .
6). 6. The metal-deposited film coating composition according to 5 above, wherein the component (c-1) is an aromatic castor oil-based polyol (c-1-1-1) having a hydroxyl value of 40 to 330 mgKOH / g. .
7. The component (c-2) is a castor oil-based polyol (c-2-1) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g. The coating for metal vapor deposition films as described in 2.
8). 5. The metal-deposited film coating material as described in 4 above, wherein the component (c-3) is acid-modified polybutadiene or acid-modified polyisoprene.
9. 5. The metal-deposited film coating composition as described in 4 above, wherein the component (c-4) is a polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol.
10. 5. The metal-deposited film coating composition as described in 4 above, wherein the component (c-4) is a polymer (c-4-2) having a saturated skeleton having an epoxy equivalent of 500 to 700 g / mol.
11. The adherend of the coating for metal vapor deposition film is soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel sheet; polyolefin resin modified with polar group-containing compound or olefin and polar group-containing compound 11. The metal-deposited film coating material as described in any one of 1 to 10 above, wherein the coating material is magnesium; acrylonitrile-butadiene-styrene copolymer; acrylonitrile-styrene copolymer; polyester resin; or acrylic resin. .
12 12. The metal vapor deposited film paint according to any one of 1 to 11 above, which is for spray coating.
13. 13. The metal-deposited film coating material as described in 12 above, further comprising 50 to 1000 parts by mass of the organic solvent (e) with respect to a total of 100 parts by mass of the components (a) to (c).
14 13. The metal-deposited film coating material as described in 12 above, further comprising 5 to 100 parts by mass of a reactive diluent (f) with respect to a total of 100 parts by mass of the components (a) to (c).
15. 15. The coating for a metal vapor deposition film according to any one of 1 to 14 above, which is used for a primer interposed between the metal vapor deposition film and the adherend.
16. 15. The coating for a metal vapor deposition film according to any one of 1 to 14 above, which is for a hard coat provided on the metal vapor deposition film.
17. (A) Vinyl ester resin or unsaturated polyester resin 10 to 40% by mass
(B) Compound having a cyclic structure and one ethylenically unsaturated group 30 to 60% by mass
(C) modifying agent 5-40% by mass,
(However, the total of the components (a) to (c) is 100% by mass)
And (d) an initiator layer (A1) of a primer comprising a metal deposition paint containing 0.1 to 15 parts by mass with respect to a total of 100 parts by mass of the components (a) to (c),
Soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel sheet; polyolefin resin modified with polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer An acrylonitrile-styrene copolymer; a polyester resin; or an acrylic resin adherend layer (B), and a metal vapor-deposited film (C);
Are stacked in the order of (C)-(A1)-(B).
18. (A) Vinyl ester resin or unsaturated polyester resin 10 to 40% by mass
(B) Compound having a cyclic structure and one ethylenically unsaturated group 30 to 60% by mass
(C) modifying agent 5-40% by mass,
(However, the total of the components (a) to (c) is 100% by mass)
And (d) an initiator, a hard coat layer (A2) comprising a metal deposition paint containing 0.1 to 15 parts by mass with respect to a total of 100 parts by mass of the components (a) to (c),
Soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel sheet; polyolefin resin modified with polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer An acrylonitrile-styrene copolymer; a polyester resin; or an acrylic resin adherend layer (B), and a metal vapor-deposited film (C);
Are stacked in the order of (A2)-(C)-(B).

Since the coating for a metal vapor deposition film according to the present invention contains the components (a), (b), (c) and (d) in a specific quantitative relationship, polar resins, ceramics, metals, etc. In particular, soft and hard vinyl chloride resins; polystyrene; polycarbonate; glass; aluminum; steel plates (for example, cold rolled steel plates, hot rolled steel plates, etc.); polyolefin resins modified with polar group-containing compounds or olefins and polar groups Copolymer with compound; Magnesium; Excellent for acrylonitrile-butadiene-styrene copolymer; acrylonitrile-styrene copolymer; polyester resin; or acrylic resin layer (hereinafter sometimes referred to as specific adherend) Adhesion with metal deposition film, moisture resistance, scratch resistance, paintability, decoration, transparency, surface smoothness, softness Sex, excellent balance of impact resistance.
The laminate according to one aspect of the present invention is a primer layer (A1) comprising a coating material for metal vapor deposition containing the components (a), (b), (c) and (d) in a specific quantitative relationship. The layer (B) of the specific adherend and the metal vapor deposition film (C) are laminated in the order of (C)-(A1)-(B). The primer layer (A1) has excellent adhesion to a specific adherend, and adhesion to a metal deposition film, moisture resistance, scratch resistance, paintability, decorating properties, transparency, surface smoothness, Since it is excellent in the balance between flexibility and impact resistance, it advantageously acts as a primer layer interposed between the layer (B) and the metal vapor deposition film (C).
A laminate according to another aspect of the present invention is a hard coat layer comprising a metal deposition paint containing the components (a), (b), (c) and (d) in a specific quantitative relationship ( This is a laminate in which A2), a specific adherend layer (B), and a metal vapor deposition film (C) are laminated in the order of (A2)-(C)-(B). The hard coat layer (A2) has an excellent balance of adhesion to metal vapor deposition film, moisture resistance, scratch resistance, paintability, decorating properties, transparency, surface smoothness, flexibility, and impact resistance. It works advantageously as a hard coat layer for a metal deposition film layer.

Hereinafter, the present invention will be described in more detail.
(A) Vinyl ester resin or unsaturated polyester resin Component (a) of the paint of the present invention is a vinyl ester resin or an unsaturated polyester resin.
The vinyl ester resin is specifically selected from a urethane (meth) acrylate resin, an epoxy (meth) acrylate resin, and a polyester (meth) acrylate resin, and more preferably has excellent flexibility and impact resistance. And urethane (meth) acrylate resin which is excellent also in adhesiveness with a specific adherend is mentioned. In addition, the (meth) acrylate referred to in the present invention refers to acrylate or methacrylate.

Such urethane (meth) acrylate resin is preferably obtained by reaction of polyol, polyisocyanate and (meth) acrylate having one or more hydroxyl groups in one molecule, and two or more (meth) acrylates in one molecule. ) It has an acryloyl group.

The polyol used in the urethane (meth) acrylate resin preferably has a number average molecular weight of 200 to 3000, particularly preferably 400 to 2000.
Typical examples of the polyol include polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, and the like. These polyols are used alone or in combination of two or more.

As used herein, the polyether polyol may include a polyol obtained by adding the alkylene oxide to bisphenol A and bisphenol F, in addition to a polyalkylene oxide such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

The polyester polyol is a condensation polymer of dibasic acids and polyhydric alcohols or a ring-opening polymer of a cyclic ester compound such as polycaprolactone. Dibasic acids used here are, for example, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, Hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2 , 3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4,4′-biphenyldicarboxylic acid, and dialkyl esters thereof. Polyhydric alcohols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3 -Butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, 1,6-hexanediol, adducts of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, Glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cycl Hexane dimethanol, paraxylene glycol, bicyclohexyl-4,4'-diol, 2,6-decalin glycol, and 2,7-decalin glycol, and the like.

Examples of the polyisocyanate used in the urethane (meth) acrylate resin include 2,4-TDI and its isomer or a mixture of isomers, MDI, HDI, IPDI, XDI, hydrogenated XDI, dicyclohexylmethane diisocyanate, tolidine diisocyanate, and naphthalene. A diisocyanate, a triphenylmethane triisocyanate, etc. can be mentioned, These can be used individually or in mixture of 2 or more types.

Examples of the (meth) acrylate (hydroxyl group-containing (meth) acrylate) having one or more hydroxyl groups per molecule used in the urethane (meth) acrylate resin include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Mono (meth) acrylates such as (meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, tris (hydroxyethyl) isocyanuric acid di (meth) acrylate, And polyvalent (meth) acrylates such as pentaerythritol tri (meth) acrylate.

Examples of the method for producing the urethane (meth) acrylate resin include: (1) First, a polyisocyanate and a polyol are preferably reacted at NCO / OH = 1.3 to 2 to form a terminal isocyanate compound, and then a hydroxyl group is produced. A method of reacting the containing (meth) acrylate so that the hydroxyl groups are approximately equal to the isocyanate group, and (2) reacting the polyisocyanate compound and the hydroxyl-containing (meth) acrylate at NCO / OH = 2 or more, Examples include a method in which a compound of a terminal isocyanate is produced and then a polyol is added to react.

The epoxy (meth) acrylate resin used as the vinyl ester resin preferably has two or more (meth) acryloyl groups in one molecule, and is an esterification catalyst for epoxy resin and unsaturated monobasic acid. It is obtained by reacting in the presence of.

Examples of the epoxy resin mentioned here include a bisphenol type or novolac type epoxy resin alone, or a resin in which a bisphenol type and a novolac type epoxy resin are mixed, and the average epoxy equivalent is preferably 150 to It is in the range of 450.

Here, as a typical example of the bisphenol type epoxy resin, a glycidyl ether type epoxy resin substantially having two or more epoxy groups in one molecule obtained by the reaction of epichlorohydrin and bisphenol A or bisphenol F is used. An epoxy resin, a methyl glycidyl ether-type epoxy resin obtained by reaction of methyl epichlorohydrin and bisphenol A or bisphenol F, an epoxy resin obtained from an alkylene oxide adduct of bisphenol A and epichlorohydrin or methyl epichlorohydrin, or the like. Typical examples of the novolak type epoxy resin include an epoxy resin obtained by a reaction of phenol novolak or cresol novolak with epichlorohydrin or methyl epichlorohydrin.

Typical examples of unsaturated monobasic acids used for epoxy (meth) acrylate resins include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl maleate, monopropyl maleate, and monoester maleate. (2-ethylhexyl) or sorbic acid. These unsaturated monobasic acids may be used alone or in combination of two or more. The reaction between the epoxy resin and the unsaturated monobasic acid is preferably carried out using an esterification catalyst at a temperature of 60 to 140 ° C., particularly preferably 80 to 120 ° C.

As the esterification catalyst, known catalysts such as tertiary amines such as triethylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline or diazabicyclooctane, triphenylphosphine or diethylamine hydrochloride Can be used as is.

The polyester (meth) acrylate resin used as the vinyl ester resin is a saturated or unsaturated polyester having two or more (meth) acryloyl groups in one molecule, and (meth) acrylic at the end of the saturated or unsaturated polyester. A compound is reacted. The number average molecular weight of such a resin is preferably 500 to 5,000.

The saturated polyester used in the present invention is a condensation reaction between a saturated dibasic acid and a polyhydric alcohol, and the unsaturated polyester is a dibasic acid containing an α, β-unsaturated dibasic acid and a polyhydric alcohol. It is obtained by the condensation reaction. In addition, the resin which made the terminal of unsaturated polyester react with the (meth) acryl compound shall be contained in vinyl ester resin in this invention, and shall be distinguished from the unsaturated polyester resin demonstrated below.

Examples of the saturated dibasic acid herein include the compounds shown in the above-mentioned polyester polyol, and examples of the α, β-unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, and itaconic acid. And itaconic anhydride. Moreover, the compound shown to the term of the said polyester polyol can be mentioned also about polyhydric alcohol.

The (meth) acrylic compound of the polyester (meth) acrylate resin used as the vinyl ester resin includes unsaturated glycidyl compounds, various unsaturated monobasic acids such as acrylic acid or methacrylic acid, and glycidyl esters thereof. is there. Preferably, glycidyl (meth) acrylate is used.

The unsaturated polyester resin is obtained by polycondensing an acid component and an alcohol component by a known method, and the kind thereof is not particularly limited as long as it is known as a thermosetting resin. . As the acid component, for example, unsaturated dibasic acids such as maleic anhydride, maleic acid, fumaric acid and itaconic acid are used. If necessary, use a saturated dibasic acid such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, and sebacic acid, and acids other than dibasic acids such as benzoic acid and trimellitic acid. be able to. Examples of the alcohol component include polyhydric alcohols shown in the above-mentioned polyester polyol section.

(B) Compound having a cyclic structure and one ethylenically unsaturated group Component (b) used in the present invention is a compound having a cyclic structure and one ethylenically unsaturated group.
Examples of the component (b) include alicyclic structure-containing (meth) acrylates such as isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and dicyclopentanyl (meth) acrylate; Examples include benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, vinylimidazole, vinylpyridine and the like.
Furthermore, compounds represented by the following formulas (1) to (3) can be given.

(Wherein R ² represents a hydrogen atom or a methyl group, R ³ represents an alkylene group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms, R ⁴ represents a hydrogen atom or a methyl group, and p is preferably Shows the number from 1 to 4.)

(Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are independent of each other and are H or CH ₃ , and q is an integer of 1 to 5)

Examples of the component (b) include monomers having an N-vinyl group in terms of excellent adhesion to metals, engineering plastics and ceramics. For example, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide. , N-vinylimidazole, N-vinylcarbazole and the like. Among these, N-vinylcaprolactam is preferable in terms of excellent metal adhesion, viscosity-reducing properties, safety, impact resistance, and flexibility.
Such a monomer having an N-vinyl group serves as a reactive diluent and improves the curing rate of the composition by blending an appropriate amount.

(C) Denaturant Component (c) used in the present invention is a denaturant.
Examples of the modifying agent (c) include (i) a polyol (c-1) having a hydroxyl value of 40 to 330 mg KOH / g.
When,
(I) a polyol having a hydroxyl value of 40 to 330 mg KOH / g and (ii) an acid value of 2 to 20 mg KOH / g (c-2)
Modified rubber (c-3),
Examples thereof include compound (c-4) having an epoxy equivalent of 150 to 700 g / mol.
Is mentioned.

(I) The polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g will be described.

The hydroxyl value of component (c) contributes to selective adhesion improvement for the specific adherend.

The (i) polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g includes aromatic, aliphatic, polybutadiene, castor oil, polyisoprene, and the like. As long as it is any type, the selective adhesive force to the specific adherend is good.
(I) The hydroxyl value is preferably 40 to 330 mgKOH / g from the viewpoint of the selective adhesive strength, and more preferably 150 to 300 mgKOH / g.

(I) As a polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g, it is more preferable in terms of selective adhesive strength to a specific adherend,
(I) Castor oil-based polyol (c-1-1) having a hydroxyl value of 40 to 330 mgKOH / g
(I) Polybutadiene-based polyol (c-1-2) having a hydroxyl value of 40 to 330 mgKOH / g
(I) Polyisoprene polyol having a hydroxyl value of 40 to 330 mgKOH / g or a hydrogenated product thereof (c-1-3)
(I) Epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g
Is mentioned.

In the present invention, the polyol of component (c) can be used as a mixture of two or more if necessary.

(I) A castor oil-based polyol (c-1-1) having a hydroxyl value of 40 to 330 mgKOH / g will be described.

The “castor oil” is an oil containing a triester compound of ricinoleic acid and glycerin. Usually, it is a natural fat or oil or a processed natural fat or oil, but it may be a synthetic fat or oil if it contains the above compounds. The ricinoleic acid constituting the triester compound contained in this castor oil is preferably contained in an amount of 90 mol% or more of the fatty acids constituting the whole triester compound. Further, the castor oil may be a processed product such as a hydrogenated product (usually hydrogenated to an intercarbon unsaturated bond in the ricinoleic acid skeleton). Usually, castor oil contains 90 mol% or more (including 100 mol%) of the above-described triester compound (in the case of a hydrogenated product, a hydrogenated product of the triester compound).

The “castor oil-based polyol” is an ester compound of ricinoleic acid and / or hydrogenated ricinoleic acid and a polyhydric alcohol. If it has this structure, it may be a polyol obtained by using castor oil as a starting material, or a polyol obtained by using a raw material other than castor oil as a starting material. This polyhydric alcohol is not particularly limited.

Castor oil-based polyols include polyols derived from castor oil and polyols obtained by modifying castor oil.

The polyol derived from castor oil is a glycerin ester in which part of the ricinoleic acid is replaced with oleic acid, and ricinoleic acid obtained by saponifying castor oil is esterified with trimethylolpropane or other short molecular polyols. These are fatty acid ester polyols derived from castor oil, such as a mixture of these and castor oil.

Examples of polyols obtained by modifying castor oil include vegetable oil-modified polyols and modified polyols having an aromatic skeleton (such as bisphenol A). A vegetable oil-modified polyol is obtained by replacing a part of glycerin ester ricinoleic acid with a fatty acid obtained from other plants, for example, higher fatty acids such as linoleic acid, linolenic acid, oleic acid obtained from soybean oil, rapeseed oil, olive oil, etc. It is obtained.

Among the castor oil-based polyols, castor oil-based polyol (c-1-1) having a component (i) hydroxyl value of 40 to 330 mgKOH / g is preferable from the viewpoint of the effect of the present invention.
Furthermore, (i) an aromatic castor oil-based polyol (c) having a hydroxyl value of 40 to 330 mgKOH / g in terms of improving the toughness (impact resistance), flexibility, and adhesion to a specific adherend. 1-1-1) is preferred. More preferably, it is 150 to 240 mg KOH / g.

The component (c-1-1-1) is a modified polyol derived from castor oil having an aromatic skeleton (for example, bisphenol A). The component (c-1-1-1) is commercially available, and examples thereof include “URIC AC series” (Ito Oil Co., Ltd.). Among these, an adduct obtained by adding polyalkylene glycol and bisphenol A to ricinoleic acid has preferable adhesion to a specific adherend, and can be represented by, for example, the following formula (4).

In the formula (4), m represents an average number of 2 to 5, and n represents an average number of 2 to 5.

Modified polyols derived from castor oil represented by the formula (4) are, for example, trade names URIC AC-005 (hydroxyl value 194 to 214 mgKOH / mg, viscosity 700 to 1500 mPa · s / 25 ° C.), AC-006 ( Hydroxyl value 168 to 187 mgKOH / mg, viscosity 3000 to 5000 mPa · s / 25 ° C., AC-008 (hydroxyl value 180 mgKOH / mg, viscosity 1600 mPa · s / 25 ° C.), AC-009 (hydroxyl value 225 mgKOH / mg, viscosity 1500 mPa -It can obtain from Ito Oil Co., Ltd. as s / 25 degreeC.

(I) A polybutadiene-based polyol (c-1-2) having a hydroxyl value of 40 to 330 mgKOH / g will be described.

Examples of the polybutadiene-based polyol used in the present invention include homopolymers such as 1,2-polybutadiene polyol and 1,4-polybutadiene polyol, poly (pentadiene / butadiene) polyol, poly (butadiene / styrene) polyol, poly ( Examples thereof include copolymers such as butadiene / acrylonitrile) polyols, and hydrogenated polybutadiene-based polyols obtained by adding hydrogen to these polyols.
Polybutadiene-based polyols are commercially available. For example, “Poly bd R-15HT (hydroxyl value 102.7 mgKOH / mg, Mw1200)” and “Poly bd R-45HT (hydroxyl value 46.6 mgKOH / manufactured by Idemitsu Kosan Co., Ltd.) are available. mg, Mw2800) "and the like.
In view of the effects of the present invention, the hydroxyl value of the (c-1-2) polybutadiene-based polyol is preferably 40 to 330 mgKOH / g, more preferably 40 to 110 mgKOH / g.
(C-1-2) The weight average molecular weight (GPC method) of the polybutadiene-based polyol is preferably 50 to 3000, and more preferably 800 to 1500.

(I) A polyisoprene-based polyol having a hydroxyl value of 40 to 330 mgKOH / g or a hydrogenated product thereof (c-1-3) will be described.

Examples of such component (c-1-3) include Polyip (registered trademark) (hydroxyl-terminated liquid polyisoprene) manufactured by Idemitsu. “Poly ip (registered trademark)” (hydroxyl value 46.6 mg KOH / mg, Mn 2500) is a polyisoprene type liquid polymer having a highly reactive hydroxyl group at the molecular end.
An example of the hydrogenated product is Epole (registered trademark) (hydroxyl-terminated liquid polyolefin) manufactured by Idemitsu. “Epol®” (hydroxyl value 50.5 mg KOH / mg, Mn 2500) is a liquid polyolefin obtained by hydrogenating “Poly ip®”. Almost no double bonds remain in the molecule.

(I) Epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g

(I) The epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g used in the present invention is obtained by reacting an epoxy resin with an active hydrogen compound.

Examples of the epoxy resin used here include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis ( Orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4- Hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobis Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as enol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, bisphenol A novolak, bisphenol F novolak, terpene diphenol; Polyglycidyl ether compound of ethylene oxide and / or propylene oxide adduct of the above mononuclear polyhydric phenol compound or polynuclear polyphenol compound; polyglycidyl ether compound of hydrogenated mononuclear polyhydric phenol compound; ethylene glycol, propylene glycol , Butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, Polyglycidyl ethers of polyhydric alcohols such as methylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacin Acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, aliphatic such as endomethylenetetrahydrophthalic acid, aromatic or Homopolymers or copolymers of glycidyl esters of alicyclic polybasic acids and glycidyl methacrylate; glycidyl such as N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane Has an amino group Epoxy compounds; vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxy Epoxidized products of cyclic olefin compounds such as bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymer, triglycidyl isocyanate And heterocyclic compounds such as nurate. In addition, these epoxy resins may be internally crosslinked by a prepolymer of terminal isocyanate.

Among these epoxy resins, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol (bisphenol AD), isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, Use of bisphenol-type epoxy resins such as polyglycidyl ether compounds such as 1,3-bis (4-hydroxycumylbenzene) and 1,4-bis (4-hydroxycumylbenzene) It is preferable because an excellent coating film can be formed.

(I) An epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g is obtained by reacting an epoxy group of the epoxy resin with an active hydrogen compound such as a carboxylic acid compound, a polyol or an amino compound. It is what

Examples of the carboxylic acid compound include acetic acid, propionic acid, 2,2-dimethylolpropionic acid, 12-hydroxystearic acid, lactic acid, butyric acid, octylic acid, ricinoleic acid, lauric acid, benzoic acid, toluic acid, cinnamic acid, phenyl Aliphatic, aromatic or cycloaliphatic monocarboxylic acids such as acetic acid and cyclohexanecarboxylic acid, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, adipic acid, dimer acid, phthalic acid, isophthalic acid, terephthalic acid, Examples include hexahydro acid and hydroxypolycarboxylic acid.

Examples of the polyol include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propylene glycol, 2,2-dimethyl-1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2,4-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 1,2-octanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, glycerin, trimethylolpropane, pentaerythritol Like low molecular weight polyols is.

Examples of the amino compounds include dialkylamine compounds such as dibutylamine and dioctylamine; alkanolamine compounds such as methylethanolamine, butylethanolamine, diethanolamine, diisopropanolamine, and dimethylaminopropylethanolamine; morpholine, piperidine, 4-methylpiperazine And heterocyclic amine compounds such as

Among the above active hydrogen compounds, alkanolamine compounds such as diethanolamine are preferable.

Also, the epoxy resin can be chain-extended with a compound having two or more active hydrogen groups such as monoethanolamine and monoisopropanolamine.

When the active hydrogen compound is reacted with the epoxy resin, a normal method of adding the active hydrogen compound to the epoxy resin can be employed. For example, the presence of a known catalyst such as a tertiary amine compound or a phosphonium salt. Below, a method in which both are heated to 60 to 200 ° C. and reacted for 3 to 10 hours can be used.

(I) A preferable hydroxyl value of the epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g is 100 to 140 mgKOH / g from the viewpoint of the effect of the present invention.

Examples of the epoxy polyol resin (c-1-4) having (i) a hydroxyl value of 40 to 330 mgKOH / g include EPICLON U-125-60BT (hydroxyl value 100 to 140 mgKOH / g) manufactured by DIC Corporation.

(I) A polyol (c-2) having a hydroxyl value of 40 to 330 mgKOH / g and (ii) an acid value of 2 to 20 mgKOH / g will be described.

The polyol (c-2) having a hydroxyl value of 40 to 330 mg KOH / g and (ii) an acid value of 2 to 20 mg KOH / g is aromatic, aliphatic or castor oil-based. Even when the hydroxyl value of (i) and the acid value of (ii) are satisfied, the selective adhesion to the specific adherend is improved.
The hydroxyl value of (i) is more preferably 230 to 300 mgKOH / g.
The acid value of (ii) is more preferably 4 to 15 mg KOH / g.

If (i) and (ii) are satisfied,
As the polyol (c-2) having a hydroxyl value of 40 to 330 mgKOH / g and (ii) an acid value of 2 to 20 mgKOH / g,
(I) a castor oil-based polyol (c-2-1) having a hydroxyl value of 40 to 330 mgKOH / g and (ii) an acid value of 2 to 20 mgKOH / g
Is exemplified.

(I) A castor oil-based polyol (c-2-1) having a hydroxyl value of 40 to 330 mg KOH / g and (ii) an acid value of 2 to 20 mg KOH / g is a polyol derived from castor oil. As disclosed in JP-A-2005-89712, it contains a castor oil-based polyol derived from ricinoleic acid, an acidic phosphate ester compound having a total carbon number of 12 or more, and, if necessary, terpene phenols Polyol compositions can also be used. These can be obtained from Ito Refinery under the trade names URIC H-1262 and H2151U, for example.

The Ito Oil URIC H-1262 is a polyol containing a castor oil-based polyol and an acidic phosphate ester compound having a total carbon number of 12 or more (viscosity: 3,500 to 8,500 mPa · s / 25 ° C., hydroxyl value: 240 to 290 (unit mgKOH / g), acid value: 4 to 15 (unit mgKOH / g)), excellent adhesion to a specific adherend, particularly excellent metal adhesion and hydrolysis resistance.
The Ito Oil URIC H-2151U is a polyol containing a castor oil-based polyol, an acidic phosphate compound having 12 or more carbon atoms and terpene phenols (viscosity: 3,500 to 8,500 mPa · s / 25). ° C, hydroxyl value: 240 to 290 (unit mgKOH / g), acid value: 4 to 15 (unit mgKOH / g)), excellent adhesion to specific adherends, especially metal adhesion and hydrolysis resistance Excellent in properties.

The modified rubber (c-3) will be described.
Examples of the modified rubber (c-3) used in the present invention include (c-3-1) liquid carboxylated polyisoprene and (c-3-2) carboxylated polybutadiene.

(C-3-1) Carboxylated polyisoprene The carboxylated polyisoprene (c-3-1) used in the present invention improves adhesion when the paint of the present invention is bonded to a metal or glass substrate. Fulfills the function of
Examples of the component (c-3-1) include LIR-420 manufactured by Kuraray as maleated polyisoprene.

(C-3-2) Carboxylated polybutadiene The carboxylated polybutadiene (c) used in the present invention functions to improve the adhesive force when the coating of the present invention is bonded to a metal or glass substrate.
Component (c-3-2) is a liquid liquid which is transparent at room temperature, and has a main chain microstructure of polybutadiene consisting of vinyl 1,2-bond type, trans 1,4-bond type, cis 1,4-bond type. It is a polymer. Here, the vinyl 1,2-bond is preferably 30% by weight or less, and the vinyl 1,2-bond exceeding 30% by weight is not preferable because the storage stability of the resulting paint deteriorates. Further, the cis 1,4-bond is preferably 40% by weight or more, and if the cis 1,4-bond is less than 40% by weight, it is not preferable because the adhesiveness of the resulting paint is lowered.

The carboxylated polybutadiene (c-3-2) component is obtained by reacting liquid polybutadiene with a carboxyl group-introducing compound, and the ratio of 1,3-butadiene and carboxyl group-introducing compound constituting the liquid polybutadiene is 1,3. -80 to 98% by weight of butadiene and 2 to 20% by weight of the carboxyl group-introducing compound are preferred.

The liquid polybutadiene used in the reaction preferably has a number average molecular weight of 500 to 10,000, more preferably 1,000 to 7,000, and a wide molecular weight distribution. The liquid polybutadiene more preferably has an iodine value measured according to DIN 53241, iodine of 30 to 500 g / 100 g of substance. Furthermore, the liquid polybutadiene preferably has a molecular structure of 70 to 90% cis-double bonds, 10 to 30% trans-double bonds and 0 to 3% vinyl double bonds.

As the carboxyl group-introducing compound, an ethylenically unsaturated dicarboxy compound, for example, an ethylenically unsaturated dicarboxylic acid, its anhydride or monoester can be used. Specific examples of the compound include maleic acid, fumaric acid, itaconic acid, 3,6-tetrahydrophthalic acid, itaconic anhydride, 1,2-dimethylmaleic anhydride, monomethyl maleate or monoethyl maleate. Can be mentioned. Among these, maleic anhydride is preferable because of safety, economy and reactivity. (Maleed polybutadiene is preferred.)

Production of a polybutadiene / maleic anhydride-addition product comprising polybutadiene and maleic anhydride can be carried out by a known method.

The acid value of maleated liquid polybutadiene according to DIN ISO 3682 is preferably 50 to 120 (mgKOH / g), more preferably 70 to 90 (mgKOH / g). When the acid value is less than 50 (mgKOH / g), the adhesiveness of the obtained paint is lowered, and when it exceeds 120 (mgKOH / g), the viscosity of the obtained paint is increased and workability is lowered.

Furthermore, the maleation rate of the maleated liquid polybutadiene is related to the viscosity, but is preferably 6 to 20%, more preferably 6 to 15%, and still more preferably 7 to 10%.

Further, the viscosity (20 ° C.) of maleated liquid polybutadiene measured by DIN 53214 is preferably 3 to 16 Pa · s, more preferably 5 to 13 Pa · s, and further preferably 6 to 9 Pa · s.

In addition, maleated liquid polybutadiene has a vinyl-double bond of 30% or less, and those having a cis-double bond in the above range have higher flexibility than liquid polybutadiene in which the cis-double bond is less than the above lower limit. And has a high maleation rate (acid value) as described above. Therefore, the paint obtained is rich in adhesiveness, and since the polarity is sufficiently imparted, the paint of the present invention can be made more flexible, the flexibility can be easily adjusted, and the decoration is excellent.
Liquid polybutadiene having a cis-double bond less than the above lower limit rapidly increases in viscosity as the maleation rate increases, but those having a cis-double bond in the above range have a small increase in viscosity. Since the viscosity is low as in the above range, the reactivity is increased and workability is improved. Moreover, the paint obtained is excellent in terms of decorating properties.

Examples of commercially available maleated liquid polybutadiene include POLYVEST OC 800S (registered trademark) and 1200S manufactured by Degussa.

The compound (c-4) having an epoxy equivalent of 150 to 700 g / mol will be described.

One form of the compound (c-4) having an epoxy equivalent of 150 to 700 g / mol used in the present invention is a polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol. .

Examples of the polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol in the paint of the present invention include mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol. Polyglycidyl ether compounds: dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1, 3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2 Polyglycols of polynuclear polyhydric phenol compounds such as tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, terpene phenol Zyl ether compounds; polyglycidyl ethers of polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct Maleic acid, fumaric acid, itaconic acid, succinic acid, gluta Acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endo Homopolymers or copolymers of glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as methylenetetrahydrophthalic acid and glycidyl methacrylate; N, N-diglycidylaniline, bis (4- (N-methyl) Epoxy compounds having a glycidylamino group such as —N-glycidylamino) phenyl) methane and diglycidylorthotoluidine; vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane Epoxidized products of cyclic olefin compounds such as carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized polybutadiene, Examples thereof include epoxidized conjugated diene polymers such as epoxidized styrene-butadiene copolymer, and heterocyclic compounds such as triglycidyl isocyanurate.

Examples of the polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol used in the present invention include biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropyl Ridenbisphenol (bisphenol A), isopropylidenebis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1, Polyphenols of bisphenol compounds such as 1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, terpene diphenol Glycidyl Jill ether is more preferable in terms of the metal adhesion.

Examples of polyglycidyl ethers of bisphenol compounds having an epoxy equivalent of 150 to 250 g / mol include Adeka Resin EP-4100E (Asahi Denka Kogyo; bisphenol A diglycidyl ether, epoxy equivalent 190).

Another form of the compound (c-4) having an epoxy equivalent of 150 to 700 g / mol used in the present invention is a polyolefin polymer (c-4-2) having an epoxy equivalent of 500 to 700 g / mol. It is. A polyolefin polymer having a hydroxyl group at one end and having an epoxy group introduced is preferred. More preferably, it is liquid.

A specific example of the polymer (c-4) having an epoxy equivalent of 150 to 700 g / mol is Kuraray L-207 (same as KRATON LIQUID ™ L-207 POLYMER). L-207 has a fully saturated skeleton (epoxidized ethylene / propylene / ethylene / butylene-OH structure) having an epoxy equivalent of 590 g / mol, a hydroxyl equivalent of 7000 g / mol, and a glass transition temperature of −53 ° C. It is a coalescence and is preferable from the viewpoint of metal adhesion as a reason for use in the present invention.

(D) Initiator The coating for metal vapor deposition film of this invention makes (d) an initiator an essential component.

In the paint of the present invention, the oligomer component (for example, vinyl ester resin or unsaturated polyester resin (a)) has a double bond such as a (meth) acryloyl group. Therefore, by adding a thermal polymerization initiator, If a photopolymerization initiator is added, it can be easily cured in a short time by ultraviolet irradiation or electron beam irradiation using an ultraviolet fluorescent lamp or a high-pressure mercury lamp. When it is desired to avoid heating the adherend and the paint, ultraviolet irradiation is preferred.

When the coating of the present invention is cured by heating, it can be cured by heating at a temperature of about room temperature to 90 ° C.
Examples of the thermal polymerization initiator include benzoyl peroxide, lauroyl peroxide, succinic acid peroxide, methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, and cyclohexanone peroxide. Is mentioned. For example, when the (1 minute) half-life temperature of the peroxides is 100 ° C. to 180 ° C., sufficient curability can be obtained at 80 ° C. × 10 minutes to 160 ° C. × 5 minutes.

Examples of the photopolymerization initiator include benzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, acetophenone, benzoin, benzoin ethyl ether, benzoin-n-propyl ether, benzoin isopropyl ether, benzoin-n- Butyl ether, benzoin isobutyl ether, benzyl-1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl 1-phenylpropan-1-one, benzyl sulfide, thioxanthone Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-chlorothixant and the like.

Organic solvent (e)
The paint of the present invention may further contain (e) an organic solvent from the viewpoint of spray coating properties. (E) By mix | blending an organic solvent, while the composition becomes low viscosity, favorable spray coating property is obtained. (E) Organic solvents include, for example, aromatic hydrocarbons such as toluene, xylene, or benzene; aliphatic hydrocarbons such as n-heptane, n-hexane, or n-octane; petroleum benzine, petroleum ether, ligroin Hydrocarbon mixtures with boiling points in the range of 30-300 ° C., such as mineral split, petroleum naphtha or kerosene; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane or ethylcyclohexane; methanol, ethanol, n- Propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, isopentanol, n-hexanol, n-octanol, 2-ethylhexanol, cyclohexanol, ethylene glycol monoethyl Alcohols such as ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether or propylene glycol monoethyl ether; ethers such as dimethoxyethane, tetrahydrofuran, dioxane, diisopropyl ether or di-n-butyl ether; acetone, Ketones such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), isobutyl ketone or isophorone; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate Or esters such as ethylene glycol monobutyl ether acetate; or chloroform , Chlorinated hydrocarbons such as methylene chloride, carbon tetrachloride, trichloroethane or tetrachloroethane, N-methylpyrrolidone (NMP), dimethylformamide, diethylacetamide or ethylene carbonate (EC), propylene carbonate ( PC) and dimethyl carbonate (DMC).

Also, preferred examples include methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK) which are excellent in volatility.

Reactive diluent (f)
The component (f) reactive diluent of the paint of the present invention is specifically a monomer having (f-1) vinyl group and / or (meth) acryloyl group.

(F-1) Monomer having vinyl group and / or (meth) acryloyl group Component (f-1) of the coating material of the present invention is a monomer having a vinyl group and / or (meth) acryloyl group.
Component (f-1) A monomer having a vinyl group and / or (meth) acryloyl group has functions of lowering viscosity and improving spray coating properties.
Specific examples include, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tricyclodecane dimethanol di (Meth) acrylate, dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), PO-modified neopentyl glycol diacrylate, modified vinyl Phenol A diacrylate and the like can be mentioned.

Others include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) ) Acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) ) Acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isode (Meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, Phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (Meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentanyl ( ) Acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, vinyl ethers, triethylene glycol divinyl ether, hydroxybutyl vinyl ether, lauryl vinyl ether Cetyl vinyl ether, 2-ethylhexyl vinyl ether, and the like.

In particular, the viscosity at 25 ° C. of component (f-1) is preferably 110 mPa · s or less, and more preferably 50 mPa · s or less, from the viewpoint of lowering the viscosity. The component (f-1) preferred in the present invention is specifically trimethylolpropane tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol divinyl ether, dipropylene glycol diacrylate, Propylene glycol diacrylate.
The viscosity was measured according to JIS K7233 using a total TVC-7 rotational viscometer at 25 ° C. The unit was mPa · S.

As said commercial item,
SR238NS (manufactured by Sartomer), 1,6-hexanediol diacrylate (HDDA), 25 ° C. viscosity = 9 mPa · s, number of functional groups = 2, fast curing, low volatility, Class 4 3 stone, skin irritation (PII ) = 4.1
SR351NS (manufactured by Sartomer), trimethylolpropane triacrylate, 25 ° C viscosity = 106 mPa · s, number of functional groups = 3, fast-curing, low volatility, type 4 3 stone, skin irritation (PII) = 3.0
DVE-3 (manufactured by BASF), triethylene glycol divinyl ether, 25 ° C. viscosity = 2.6 mPa · s
Dipropylene glycol diacrylate (BASF) 25 ° C. viscosity = 10 mPa · s
Tripropylene glycol diacrylate (manufactured by BASF) 25 ° C. viscosity = 20 mPa · s
Is mentioned.

(Composition ratio of paint for metal vapor deposition film)
In the coating for a metal vapor deposition film of the present invention, the component (a) is blended in an amount of 10 to 40% by mass from the viewpoints of adhesion, flexibility and impact resistance. A more preferable blending ratio of the component (a) is 15 to 35% by mass in terms of a viscosity that is easy to process.
When the compounding amount of component (a) exceeds 40% by mass, the adhesion to the specific adherend and the metal vapor-deposited film deteriorates, and the workability deteriorates due to thickening. On the other hand, when the content is less than 10% by mass, the adhesion to the specific adherend and the metal vapor-deposited film, flexibility, and impact resistance are lowered.

In the coating for a metal vapor deposition film of the present invention, the component (b) is blended in an amount of 30 to 60% by mass from the viewpoint of adhesion to the specific adherend and the metal vapor deposition film, flexibility, and impact resistance. A more preferable amount of component (b) is 40 to 55% by mass from the viewpoint of easy processing viscosity.
When the compounding amount of the component (b) exceeds 60% by mass, the adhesion to the specific adherend and the metal vapor-deposited film, flexibility, and impact resistance are deteriorated. On the other hand, if it is less than 30% by mass, the adhesion to the specific adherend and the metal vapor-deposited film, the flexibility and the impact resistance are deteriorated, and the workability is lowered due to the thickening.

In the coating for metal vapor deposition film of the present invention, the component (c) is blended in an amount of 5 to 40% by mass from the viewpoints of adhesiveness and flexibility. A more preferable component (c) content is 10 to 30% by mass, particularly preferably 10% in terms of adhesion to a specific adherend and a metal vapor-deposited film, toughness (impact resistance), and bleed resistance. To 25% by mass.
When the compounding amount of the component (c) exceeds 40% by mass, the toughness (impact resistance) is lowered due to the deterioration of the bleed resistance, and the adhesion to the specific adherend and the metal deposited film is also lowered. On the other hand, when the content is less than 5% by mass, the adhesion to the specific adherend and the metal vapor-deposited film, flexibility, and impact resistance are deteriorated.

In the coating for metal vapor deposition film according to the present invention, the component (d) is a component of the above components (a) to (c) from the viewpoint of practical photocuring time (irradiation intensity of 500 mJ / cm ² and irradiation for 10 seconds or less). 0.1 to 15 parts by mass is blended with respect to a total of 100 parts by mass. The amount of the component (d) is more preferably 1 to 10 parts by mass, particularly preferably 2 to 5 parts by mass in terms of practical photocuring time (irradiation intensity of 500 mJ / cm ² for 3 seconds or less). Part.
When the compounding amount of component (d) exceeds 15 parts by mass, flexibility, adhesion to a specific adherend and a metal vapor deposition film, and impact resistance are lowered. Moreover, if it is less than 0.1 mass part, since photocuring is inadequate, it is inferior to the adherend to a specific adherend and a metal vapor deposition film. In addition, also when using a thermal-polymerization initiator, the same compounding quantity as the above may be sufficient.

In the coating for a metal deposited film of the present invention, the component (e) is blended in an amount of 50 to 1000 parts by mass with respect to a total of 100 parts by mass of the components (a) to (c) from the viewpoint of spray coating properties.
A more preferable amount of component (e) is 600 to 1000 parts by mass from the viewpoint of spray coating properties.

In the coating for a metal deposited film of the present invention, the component (f) is blended in an amount of 5 to 100 parts by mass with respect to a total of 100 parts by mass of the components (a) to (c) from the viewpoint of spray coating properties.
A more preferable amount of component (e) is 40 to 70 parts by mass from the viewpoint of spray coating properties.

In the coating for a metal vapor deposition film of the present invention, a functional filler or the like generally used as a filler can be added and blended as necessary within a range not impairing the object of the present invention.

Examples of imparting rigidity include talc and mica, and these are used singly or in combination of two or more.

Examples of thermal conductivity imparting include barium sulfate and magnesium oxide, and these are used alone or in combination of two or more.

Examples of imparting thermal expansion include thermal expansion microcapsules.
Examples of the leveling property imparting include a silicone leveling agent.

Further, the viscosity at 25 ° C. of the metal vapor deposited film paint of the present invention is not particularly limited, but it is preferably 3,000 mPa · s or less, more preferably 100 to 2,000 mPa · s. If the viscosity is within this range, stable storage stability that does not separate with time changes is obtained, bubbles are not easily generated, and smooth surface properties can be obtained.粘度 The viscosity can be measured with a B-type viscometer.

As a method for preparing the paint, for example, the component (a) is first put in a container equipped with a stirrer, and then the component (b) is added thereto and sufficiently stirred at room temperature. If the viscosity is too high, stirring may be performed while heating at 100 ° C. or lower. If it exceeds 100 ° C., the vapor generation of the component (b) becomes remarkable, which is not preferable in the working environment. Thereafter, after adding component (c) and stirring, when the liquid temperature reaches room temperature, component (d) is added, and the mixture is sufficiently stirred so as not to remain undissolved.
When adding other components, add them at the end and stir well.
The coating material for metal vapor deposition of the present invention obtained by stirring is quickly processed or stored in a cool and dark place.

The coating for metal vapor deposition film according to the present invention comprises, as an adherend, a soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel sheet; a polyolefin resin or olefin modified with a polar group-containing compound and a polar group-containing compound. Magnesium; acrylonitrile-butadiene-styrene copolymer; acrylonitrile-styrene copolymer; polyester resin (eg, polyethylene terephthalate (PET), polybutylene terephthalate, etc.); or acrylic resin (eg, PMMA); Adhesiveness to a metal vapor deposition film is particularly good. The coating for metal vapor deposition film which has favorable adhesiveness with respect to these adherends is not disclosed in the prior art.
The polyolefin resin modified with a polar group-containing compound is a polyolefin into which polar groups such as —OH, —NO ₂ , —CO, —NH ₂ , —NH, —OCH ₃ , —SO ₃ H and the like are introduced. Examples thereof include polyolefin resins grafted with at least one selected from maleic anhydride and glycidyl methacrylate, and specific examples include polyethylene and polypropylene grafted with maleic anhydride, and polyethylene and polypropylene grafted with glycidyl methacrylate. . Copolymers of olefins and polar group-containing compounds include, for example, copolymers of ethylene and vinyl acetate (EVA), copolymers of ethylene and (meth) acrylic acid (EAA, EMA, etc.), ethylene and A copolymer (EEA etc.) with (meth) acrylic acid ester is mentioned.

Among the above-mentioned specific adherends, polycarbonate, acrylonitrile-butadiene-styrene copolymer and acrylic resin are preferable from the viewpoint of adhesiveness.

The metal vapor deposition film can be, for example, a vapor deposition film formed by a known vacuum vapor deposition method, and examples of the metal include Al, Cu, Cr, Au, Ag, and the like. Has particularly high adhesion to an Al deposited film.

(Laminated body of the present invention and coating method-1)
In the coating method-1 of the present invention, as the process I, the metal vapor deposition coating material of the present invention is prepared as described above, and subsequently, as the process II, the metal vapor deposition is performed on the layer (B) of the specific adherend. A film coating is laminated to form a primer layer (A1) made of a metal vapor deposition paint, and as a step III, a metal vapor deposition film (C) is further laminated. According to the coating method-1 of the present invention, the adhesion of the three layers (C)-(A1)-(B) becomes strong.
The thickness of the primer layer (A1) (cured coating film) is not particularly limited, but is about 2 to 50 μm, preferably about 5 to 30 μm, and more preferably about 8 to 20 μm. (When the primer layer (A1) in the present invention is blended without a solvent, the coating thickness and the film thickness after curing are not significantly different because there is little shrinkage during curing.) By adjusting to this coating film thickness, It is excellent in transparency, can reduce the strength of warping of the resin molded body due to cure shrinkage, and can prevent the surface hardness from being lowered due to uncured binder resin components. As the primer layer (A1) coating method, spin coating method, (doctor) knife coating method, micro gravure coating method, direct gravure coating method, offset gravure method, reverse gravure method, reverse roll coating method, (Meyer) Methods such as bar coating, die coating, spray coating, and dip coating can be preferably applied. Preferably, a spray coating method is used.

(Laminated body of the present invention and coating method 2 thereof)
In the coating method-2 of the present invention, as the process I, the metal-deposited film coating material of the present invention is prepared as described above. Subsequently, as the process II, on the layer (B) of the specific adherend (during this time) A known undercoat (primer) layer may be laminated), and a metal vapor-deposited film (C) is laminated. Step III includes a step of laminating a metal vapor deposition coating on the metal vapor deposition film (C) to form a hard coat layer (A2) made of the metal vapor deposition coating. According to such a coating method-2 of the present invention, the adhesion of the three layers (A2)-(C)-(B) becomes strong.
The thickness of the hard coat layer (A2) (cured coating film) is not particularly limited, but is, for example, 0.5 to 20 μm, preferably 1.5 to 10 μm, and more preferably 2.0 to 10 μm. As the coating method of the hard coat layer (A2), spin coating method, (doctor) knife coating method, micro gravure coating method, direct gravure coating method, offset gravure method, reverse gravure method, reverse roll coating method, (Meyer ) Bar coating method, die coating method, spray coating method, dip coating method and the like can be preferably applied. Preferably, a spray coating method is used.

Hereinafter, the present invention will be further described with reference to examples and comparative examples, but the present invention is not limited to the following examples.

The raw materials used in the examples and comparative examples are as follows.
Component (a-1) Vinyl ester resin (i) Urethane acrylate Sartomer CN963B80 Urethane acrylate (HDDA blend), Type = Polyester, 60 ° C. viscosity = 1,100, Number of functional groups = 2
(Ii) Polyester acrylate CN292 polyester acrylate manufactured by Sartomer, type = aliphatic polyester, viscosity at 25 ° C. = 630, number of functional groups = 4
(Iii) Epoxy acrylate Sartomer CNUVE151 epoxy acrylate, type = polyester, viscosity at 25 ° C. = 150,000, number of functional groups = 2
(Iv) Aliphatic urethane acrylate manufactured by Sartomer CN966J75 Aliphatic urethane acrylate (IBOA blend), type = polyester, 60 ° C. viscosity = 4,240, 25 ° C. viscosity = 105,000, number of functional groups = 2
Component (a-2) Unsaturated polyester resin RIGOLAC 21E-A-2 (trademark) manufactured by Showa Polymer Co., Ltd.
Component (a-3) Vinyl ester resin, manufactured by Showa Polymer Co., Ltd., RIPOXY VR-77 (trademark)
Viscosity: 1,000 (dPa · s / 25 ° C)
Molecular weight: 510

Component (b) Compound having a cyclic structure and one ethylenically unsaturated group (i) Nippon Shokubai Co., Ltd., N-vinylpyrrolidone Molecular weight: 111.14
Boiling point 219 ° C
Vapor pressure (24 ℃) 0.10mm Hg
Flash point 98 ° C
Viscosity (25 ° C) 2 cps
Melting point 13 ° C
(Ii) NSF-caprolactam boiling point 117 ° C (10mm Hg) manufactured by BASF
Vapor pressure <0.1 mm Hg (20 ℃)
Flash point 110 ° C
Melting point 35 ℃
Viscosity 3.5 cps (40 ° C)

Component (c) Modifier (c-1-2) Polybutadiene polyol manufactured by Idemitsu Kosan Co., Ltd., Poly bd R-15HT
Viscosity: 1.5 Pa · s / 30 ° C., hydroxyl value: 102.7 mg KOH / g
(C-1-1-1) Aromatic castor oil-based polyol manufactured by Ito Oil Co., Ltd., URIC (trademark) AC-006, a polyol derived from castor oil represented by the above formula (4), viscosity: 0.7 to 1.5 Pa · s / 25 ° C., hydroxyl value: 194 to 214 mg KOH / g
(C-1-3) Polyisoprene-based polyol manufactured by Idemitsu Kosan Co., Ltd. Polyisoprene type liquid polymer having a highly reactive hydroxyl group at the molecular end (hydroxyl value 46.6 mgKOH / mg, number average) Molecular weight Mn = 2500)
(C-2-1) Castor oil-based polyol Ito Oil URIC H-1262
Polyol containing a castor oil-based polyol and an acidic phosphate ester compound having a total carbon number of 12 or more Viscosity: 3,500 to 8,500 Pa · s / 25 ° C., acid value: 4 to 15 (unit mgKOH / g), hydroxyl value : 240-290 (unit mgKOH / g)
(C-2-1) Castor oil-based polyol Ito Oil URIC H-2151U
A polyol containing a castor oil-based polyol, an acidic phosphate ester compound having 12 or more carbon atoms and terpene phenols Viscosity: 3,500 to 8,500 Pa · s / 25 ° C., acid value: 4 to 15 (unit: mgKOH / g), hydroxyl value: 240 to 290 (unit: mgKOH / g)
(C-1-3) Hydrogenated polyisoprene polyol manufactured by Idemitsu Kosan Co., Ltd. Epol (trademark) hydroxyl terminated liquid polyolefin (viscosity (Pa · s / 30 ° C) 75, hydroxyl value (mgKOH / g) 50.5, number average Molecular weight 2500)
(C-3-1) Maleinized polyisoprene Kuraray LIR-420 (acid value (mgKOH / g) 40)
(C-3-2) Maleic acid-modified polybutadiene
SARTOMER Ricon130MA8 (viscosity (Pa · s / 30 ° C) 6.5, acid value (mgKOH / g) 46, number average molecular weight 2700)
(C-3-2) Maleic acid-modified polybutadiene
POLYVEST ™ OC 800 S manufactured by EVONIK (1,4-cis double bond in polybutadiene: 75%, 1,4-trans double bond: 24%, vinyl bond: 1%, maleation ratio: 7.5 %, Number average molecular weight: 3300 (GPC), weight average molecular weight: 13,600 (GPC), viscosity (20 ° C.): 6 to 9 Pa · s (measured with DIN 53214), acid value: 70 to 90 mg KOH / g, iodine Value: 380 to 420 g / 100 g, (polymerized with Ziegler-Natta catalyst)
(C-1-4) Epoxy polyol resin
DIC Corporation EPICLON (trademark) U-125-60BT
(Viscosity (Pa · s / 30 ° C) 70, hydroxyl value (mgKOH / g) 120)
(C-4-1) Polyepoxy compound Adeka Resin EP-4100E having an epoxy equivalent of 150 to 250 g / mol (Asahi Denka Kogyo; bisphenol A diglycidyl ether, epoxy equivalent 190)
(C-4-2) Polymer having a saturated skeleton having an epoxy equivalent of 500 to 700 g / mol L-207 manufactured by Kuraray (same as KRATON LIQUID ™ L-207 POLYMER) (Epoxy equivalent is 590 g / mol, Hydroxyl equivalent weight is 7000 g / mol, glass transition temperature -53 ° C, polymer with fully saturated skeleton (epoxidized ethylene / propylene / ethylene / butylene-OH structure)

The characteristics of each polyol were measured as follows.
・ Viscosity measurement method The viscometer is measured using a single cylindrical rotational viscometer (B type TVC--5) according to JIS K7117-1.
1. A 500ml beaker (standard) is used for the measuring instrument.
2. The standard rotor is selected from two types: M1 to M4 rotors for low and medium viscosity and H1 to H7 rotors for medium and high viscosity. Hydroxyl value measurement method Hydroxyl value is included in 1g of sample. This is the number of mg of potassium hydroxide required to acetylate the OH group. According to JIS K 1557-1, OH groups in the sample are acetylated using acetic anhydride, and acetic acid not used is titrated with potassium hydroxide solution.

A: Amount of 0.5 mol / l potassium hydroxide ethanol solution used for the blank test (ml)
B: 0.5mol / l potassium hydroxide ethanol solution used for titration (ml)
f: Factor

-Acid value measuring method It represents with the mg number of potassium hydroxide required to neutralize the acidic component contained in 1g of sample oils. According to JIS K 1557-5,
(1) End-point pH measurement Take 10 mL of buffer stock solution B in a 200-mL beaker, add 100 mL of titration solvent, immerse the electrode, and use the pH that changes within 0.1 pH within 30 seconds as the buffer end point.
(2) Measurement of acid value 1. Weigh accurately 20 g of sample into a 200 mL beaker.
2. Add 125mL of toluene / 2-propanol / pure water mixed solvent and titrate with 0.1mol / L potassium hydroxide titrant.
Result of (1) 11.72 Set pH as the end point and calculate the acid value by the following formula. Moreover, a blank is calculated | required in the same procedure.
Acid value (mgKOH / g) = (D−B) × K × F × M / S
D: Titration value (mL)
B: Blank (0.085mL)
K: Molecular weight of KOH (56.1)
F: Factor of titrant (1.000)
M: Molar concentration of titrant (0.1 mol / L)
S: Sampling amount (g)

Component (d) Component Initiator (i) Photopolymerization initiator CIBA, IRGACURE ™ 819, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (ii) Thermal polymerization initiator NOF Corporation Perhexa 25B (1 minute half-life: 179 ° C.), 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane

Examples 1 to 64, Comparative Examples 1 to 8
In the blending ratios (parts by mass) shown in Tables 1 to 18 below, the component (a) is placed in a container equipped with a stirrer, then the component (b) is added, and the mixture is sufficiently stirred at room temperature. After adding c) and stirring, when the liquid temperature reached room temperature, the component (d) was added, and the mixture was sufficiently stirred so as not to remain undissolved to obtain a paint. The viscosity (mPa · s) at 25 ° C. of the obtained paint was measured. That is, using a handy type digital viscometer TVC-7 type viscometer (Toki Sangyo Co., Ltd.), the viscosity at 25 ° C. was measured using an appropriate rotor (No. 0 to No. 5) according to the viscosity. The results are also shown in Tables 1 to 18.

<Evaluation as a hard coat paint provided on the metal deposition film>
Known undercoat treatment (primer treatment)
[Adjustment of undercoat material]
500 g of toluene was charged into a 2 L four-necked flask and heated to an internal temperature of 80 ° C. Next, while maintaining the internal temperature at 80 ° C. and stirring the flask, 150 g (30%) of N- (n-butoxymethyl) acrylamide, 200 g (40%) of methyl methacrylate, and 150 g of styrene ( 30%) and 1 g of azobisisobutylnitrile as a polymerization catalyst were dropped into the flask by constant-rate dropping for 2 hours. Thereafter, 0.2 g of azobisisobutylnitrile was added every 4 hours, and the mixture was stirred for 6 hours while adding 50 times of the copolymer (K) having a mass average molecular weight of 3.0 × 10 ^{4 in} terms of polystyrene by GPC measurement. % Toluene solution was obtained. 100 parts by mass of a toluene solution of copolymer (K), 30 parts by mass of DPHA (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA), EO-modified hydrogenated bisphenol A diacrylate (Daiichi Kogyo Seiyaku Co., Ltd.) Manufactured, trade name: New Frontier HBPE-4) 10 parts by mass, dicyclopentenyloxyethyl acrylate (manufactured by Hitachi Chemical Co., Ltd., trade name: funcryl FA-512A), 5 parts by weight of benzophenone, butyl acetate 80 parts by mass and 100 parts by mass of isobutanol were mixed and stirred to prepare an undercoat material.

Next, on each specific adherend (B) shown in Tables 1 to 18 (dimensions: 150 mm × 25 mm × thickness 1 mm), the film thickness after curing the above-described undercoat material is 10 to 20 μm. Spray painted. Thereafter, the test piece of the coated resin molded product was kept in a hot air dryer at 60 ° C. for 5 minutes to volatilize the organic solvent. Next, the obtained test piece was irradiated with an active energy ray having a wavelength of 340 to 380 nm and an integrated light quantity of 1,000 mJ / cm ² in air using a high pressure mercury lamp, and the film thickness after curing was about 15 to 20 μm. An undercoat layer was formed as follows.

Next, using a vacuum deposition apparatus (trade name: EBX-6D) manufactured by Nippon Vacuum Technology Co., Ltd., vacuum deposition was performed so that the aluminum film thickness was about 100 nm, and the resin film was laminated with an aluminum film on the surface. I got a product.

Thereafter, the above-prepared coating material is applied to the resin molded article by spray coating (coating thickness: 15 to 20 μm), and this is cured by irradiating with ultraviolet rays having an energy of 500 mJ / cm ² under air. A hard coat layer was formed on the substrate to prepare a laminate. When a thermal polymerization initiator was used, a laminate was prepared by adding 0 to 0.05 parts by mass of 6% naphthene cobalt to the composition as necessary.

Examples 8 and 61 are examples in which (ii) a thermal polymerization initiator was used for component (d).
On each specific adherend (B) shown in the table (dimensions: 150 mm × 25 mm × thickness 1 mm), a paint is applied by spray coating (coating thickness 15-20 μm), and this is heat-treated at 100 ° C. for 10 minutes. And cured to prepare a laminate.

Examples 65 to 128, Comparative Examples 9 to 16
In the blending proportions (parts by mass) shown in Tables 19 to 36 below, the component (a) was placed in a container equipped with a stirrer, then the component (b) was added, and the mixture was sufficiently stirred at room temperature. After adding c) and stirring, when the liquid temperature reached room temperature, the component (d) was added, and the mixture was sufficiently stirred so as not to remain undissolved to obtain a paint. The viscosity (mPa · s) at 25 ° C. of the obtained paint was measured. That is, using a handy type digital viscometer TVC-7 type viscometer (Toki Sangyo Co., Ltd.), the viscosity at 25 ° C. was measured using an appropriate rotor (No. 0 to No. 5) according to the viscosity. The results are also shown in Tables 19 to 36.

<Evaluation as a primer provided on a specific adherend>
Next, the paint is applied by spray coating method on each specific adherend (B) (dimensions: 150 mm × 25 mm × thickness 1 mm) shown in Tables 19 to 36 (applied thickness 15 to 20 μm). A laminate was prepared by irradiating and curing ultraviolet rays with energy of 500 mJ / cm ² under air. When a thermal polymerization initiator is used, if necessary, 0 to 0.05 parts by mass of 6% naphthenic cobalt is added to the composition and cured by heat treatment at 100 ° C. for 30 minutes. (B) A primer layer was formed thereon to prepare a laminate.

Examples 72 and 125 are examples in which (ii) a thermal polymerization initiator was used for component (d).
On each specific adherend (B) shown in the table (dimensions: 150 mm × 25 mm × thickness 1 mm), a paint is applied by spray coating (coating thickness 15-20 μm), and this is heat-treated at 100 ° C. for 10 minutes. And cured to prepare a laminate.

Next, using a vacuum deposition apparatus manufactured by Nippon Vacuum Technology Co., Ltd. (trade name: EBX-6D), vacuum deposition was performed on the primer layer so that the aluminum film thickness was about 100 nm. A resin molded product having a laminated film was obtained.

Each specific adherend (B) used is as follows.
・ Hard vinyl chloride resin PVC (Riken Technos, trade name Riken PVC Compound RE-3844)
-Soft vinyl chloride resin PVC (manufactured by Riken Technos, trade name Leonyl BZL6060N)
・ Polystyrene PS (Toyo Styrol GP G100C, manufactured by Toyo Styrene Co., Ltd.)
・ Polycarbonate PC (trade name Panlite L-1225L, manufactured by Teijin Chemicals Ltd.)
・ Acrylonitrile-butadiene-styrene copolymer ABS (manufactured by UMG, trade name UMG ABS EX114)
・ Acrylonitrile-styrene copolymer AS (made by Asahi Kasei Chemicals Co., Ltd., trade name Stylac-AS767)
・ PET: Unitika Unitika polyester resin MA-2103
・ PMMA: Mitsubishi Rayon Acrypet VH
・ Glass (slide glass for microscope preparation)

The other components used are as follows.
Component (e) Organic solvent / Component (e-1) MEK: Methyl ethyl ketone / Component (e-2) MIBK: Methyl isobutyl ketone component (f) Reactive diluent / component (f-1) HDDA: SR238NS (manufactured by Sartomer) ), 1,6-hexanediol diacrylate, 25 ° C. viscosity = 9 mPa · s, number of functional groups = 2, fast curing, low volatility, 4 types 3 stones, skin irritation (PII) = 4.1
Component (f-2) DVE-3: triethylene glycol divinyl ether, viscosity at 25 ° C. = 2.6 mPa · s

The obtained laminate was subjected to the following cross-cut tape test.
(Adhesion test: cross-cut tape test)
The measurement was performed as follows in accordance with the cross cut tape test method described in Japanese Industrial Standard K5400.
Cross-cut tape test (Cross-cut test, coating thickness 15-20μm (spin coating method)): 1 × 1mm square using a cutter knife on the test surface (surface layer, ie, hard coat layer or primer layer side) Make a cut on the grid. Use the cutter guide. The number of grids is 10 vertical x 10 horizontal = 100. Strongly press the cellophane tape into the grid, and peel off the end of the tape rapidly at an angle of 45 ° to see the grid pattern (number of grids remaining without peeling).
The results are also shown in Tables 1 to 36.

(Moisture resistance)
Place the above-mentioned resin molded product in a constant temperature and humidity chamber at 80 ° C. and 85% relative humidity for 24 hours, and then cross-cut to reach the specific adherend on the surface of the resin molded product, that is, the hard coat layer or primer layer side. It put with the cutter knife, a cellophane tape was stuck on it, it peeled off rapidly, the peeling state of the grid was observed, and the judgment of evaluation of moisture resistance was performed on the following references | standards. Moreover, about the thing with the adhesiveness of a grid cross, the cross-cut peeling test in said adhesive evaluation was implemented, and the presence or absence of peeling of the grid was confirmed.
“◎”: No peeling in the cross-cut peel test.
“◯”: Adhesion at the crosscut portion is good, and no peeling occurs.
“Δ”: Adhesion at the crosscut portion is slightly good, and is slightly peeled.
“×”: Adhesion of the cross cut portion is poor, and almost the entire area of the cellophane tape is peeled off.
The results are also shown in Tables 1 to 36.

(Scratch resistance)
The surface of the resin molded product, that is, the hard coat layer or the primer layer is rubbed 5 times with steel wool (# 0000, manufactured by Bonstar Co., Ltd.), and the surface of the resin molded product is visually observed for damage. The scratch resistance was evaluated according to the following criteria.
“◎”: There is no scar.
“◯”: There is a slight scar.
“△”: A scar remains clearly.
“×”: Many scars remain.
The results are also shown in Tables 1 to 36.

As is clear from the table, in the examples of the present invention, the coating for metal vapor deposition film contains the components (a), (b), (c) and (d) in a specific quantitative relationship. Therefore, it exhibited excellent adhesion to various adherends, as well as excellent moisture resistance and scratch resistance. Moreover, it was also confirmed that the balance of paintability, decorating properties, transparency, surface smoothness, flexibility, and impact resistance is excellent.
On the other hand, Comparative Examples 1 and 9 were inferior in adhesion to the specific adherend and deteriorated in moisture resistance and scratch resistance because the blending ratio of component (a) was less than the lower limit specified in the present invention.
In Comparative Examples 2 and 10, since the blending ratio of the component (a) exceeds the upper limit defined in the present invention, the adhesion to the specific adherend is inferior, and the moisture resistance and scratch resistance are deteriorated.
In Comparative Examples 3 and 11, since the blending ratio of the component (b) was less than the lower limit specified in the present invention, the adhesion to the specific adherend was inferior, and the moisture resistance and scratch resistance were deteriorated.
In Comparative Examples 4 and 12, since the blending ratio of the component (b) exceeds the upper limit defined in the present invention, the adhesiveness to the specific adherend is inferior, and the moisture resistance and scratch resistance are deteriorated.
Since Comparative Examples 5 and 13 did not contain the component (c), the adhesion to the specific adherend was inferior, and the moisture resistance and scratch resistance were deteriorated.
In Comparative Examples 6 and 14, since the blending ratio of the component (c) exceeds the upper limit defined in the present invention, the adhesion to the specific adherend is inferior, and the moisture resistance and scratch resistance are deteriorated.
In Comparative Examples 7 and 15, since the component (d) was not blended, the adhesion to the specific adherend was inferior, and the moisture resistance and scratch resistance were deteriorated.
In Comparative Examples 8 and 16, since the blending ratio of the component (d) exceeded the upper limit defined in the present invention, the adhesion to the specific adherend was inferior, and the moisture resistance and scratch resistance were deteriorated.

The coating for metal vapor deposition film of the present invention has excellent adhesion to a specific adherend, and adhesion to the metal vapor deposition film, moisture resistance, scratch resistance, paintability, decorating property, transparency, Excellent balance of surface smoothness, flexibility and impact resistance. Therefore, it is useful for the main body portion of a mobile phone, the lens portion of sunglasses, the navigation system, the main body portion of a car audio product, the housing portion of a personal computer or notebook computer, and the like.

Claims (18)

1. (A) Vinyl ester resin or unsaturated polyester resin 10 to 40% by mass
   (B) Compound having a cyclic structure and one ethylenically unsaturated group 30 to 60% by mass
   (C) modifying agent 5-40% by mass,
   (However, the total of the components (a) to (c) is 100% by mass)
   And (d) Initiator A coating for a metal vapor-deposited film comprising 0.1 to 15 parts by mass with respect to a total of 100 parts by mass of the components (a) to (c).
2. The component (a) is urethane (meth) acrylate, and the coating for metal vapor deposition film according to claim 1.
3. 3. The metal-deposited film coating composition according to claim 1, wherein the component (b) is a monomer having an N-vinyl group.
4. The component (c) is a polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g; and a polyol (c-2) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g The modified rubber (c-3) is at least one selected from the group consisting of the compound (c-4) having an epoxy equivalent of 150 to 700 g / mol. The coating for metal vapor deposition films as described in 2.
5. The component (c-1) is a castor oil-based polyol (c-1-1) having a hydroxyl value of 40 to 330 mgKOH / g; a polybutadiene-based polyol (c-1-2) having a hydroxyl value of 40 to 330 mgKOH / g; 5. The metal vapor-deposited film according to claim 4, which is at least one selected from the group consisting of a polyisoprene-based polyol having a value of 40 to 330 mg KOH / g or a hydrogenated product thereof (c-1-3). paint.
6. 6. The metal-deposited film according to claim 5, wherein the component (c-1) is an aromatic castor oil-based polyol (c-1-1-1) having a hydroxyl value of 40 to 330 mgKOH / g. paint.
7. The component (c-2) is a castor oil-based polyol (c-2-1) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g. 4. The paint for metal vapor deposition films according to 4.
8. The metal vapor deposition film coating material according to claim 4, wherein the component (c-3) is acid-modified polybutadiene or acid-modified polyisoprene.
9. The metal vapor-deposited film coating composition according to claim 4, wherein the component (c-4) is a polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol.
10. The metal-deposited film coating composition according to claim 4, wherein the component (c-4) is a polymer (c-4-2) having a saturated skeleton having an epoxy equivalent of 500 to 700 g / mol.
11. The adherend of the coating for metal vapor deposition film is soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel sheet; polyolefin resin modified with polar group-containing compound or olefin and polar group-containing compound The metal-deposited film according to any one of claims 1 to 10, which is a polymer; magnesium; acrylonitrile-butadiene-styrene copolymer; acrylonitrile-styrene copolymer; polyester resin; or acrylic resin. paint.
12. The metal-deposited film paint according to any one of claims 1 to 11, which is for spray coating.
13. 13. The metallized film paint according to claim 12, further comprising 50 to 1000 parts by mass of an organic solvent (e) with respect to 100 parts by mass in total of the components (a) to (c).
14. 13. The metal-deposited film coating material according to claim 12, further comprising a reactive diluent (f) in an amount of 5 to 100 parts by mass with respect to a total of 100 parts by mass of the components (a) to (c).
15. The metal-deposited film paint according to any one of claims 1 to 14, which is used for a primer interposed between a metal-deposited film and an adherend.
16. The metal-deposited film coating material according to any one of claims 1 to 14, which is used for a hard coat provided on a metal-deposited film.
17. (A) Vinyl ester resin or unsaturated polyester resin 10 to 40% by mass
    (B) Compound having a cyclic structure and one ethylenically unsaturated group 30 to 60% by mass
    (C) modifying agent 5-40% by mass,
    (However, the total of the components (a) to (c) is 100% by mass)
    And (d) an initiator layer (A1) of a primer comprising a metal deposition paint containing 0.1 to 15 parts by mass with respect to a total of 100 parts by mass of the components (a) to (c),
    Soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; An acrylonitrile-styrene copolymer; a polyester resin; or an acrylic resin adherend layer (B), and a metal vapor-deposited film (C);
    Are stacked in the order of (C)-(A1)-(B).
18. (A) Vinyl ester resin or unsaturated polyester resin 10 to 40% by mass
    (B) Compound having a cyclic structure and one ethylenically unsaturated group 30 to 60% by mass
    (C) modifying agent 5-40% by mass,
    (However, the total of the components (a) to (c) is 100% by mass)
    And (d) an initiator, a hard coat layer (A2) comprising a metal deposition paint containing 0.1 to 15 parts by mass with respect to a total of 100 parts by mass of the components (a) to (c),
    Soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; An acrylonitrile-styrene copolymer; a polyester resin; or an acrylic resin adherend layer (B), and a metal vapor-deposited film (C);
    Are stacked in the order of (A2)-(C)-(B).