JPH08245903A - Active energy ray curable resin composition for silver coating - Google Patents

Abstract

(57) [Summary] [Structure] 10 to 95% by weight of a saturated compound (A) having a hydrolyzable silyl group and 5 to 90% by weight of an unsaturated compound (B) having a radical-polymerizable unsaturated double bond. Containing 0.5-2,000 mmol of hydrolyzable silyl group
/ Kg contained active energy ray curable resin composition for silver coating. And 0.5 to 2,000 mmol of a hydrolyzable silyl group containing an unsaturated compound (C) having a hydrolyzable silyl group and a radically polymerizable unsaturated bond in one molecule.
/ Kg contained active energy ray curable resin composition for silver coating. [Effect] The present invention has excellent adhesion to the surface of silver, can sufficiently exhibit the spreadability and beautiful surface appearance of silver, and can prevent discoloration (corrosion) of silver. An active energy ray-curable resin composition for silver coating having excellent durability can be provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to silver products such as ornaments, tableware, electronic parts, lighting equipment, etc., which are excellent in preventing discoloration (corrosion) of silver, and particularly excellent in resistance to discoloration on a silver-deposited surface. The present invention relates to an active energy ray-curable resin composition for silver, which is suitable for coating.

[0002]

2. Description of the Related Art Silver is a noble metal and has excellent optical properties and electrochemical properties, and has been used for a long time in ornaments, coins, tableware, electronic materials, dental materials and the like. In recent years, the usage has rapidly increased as a material for lighting equipment, a material for photographic industry, a semi-conductive material, a conductive material, an aerospace material, and is widely used as an industrial material.

However, silver used for these purposes is chemically very unstable and easily reacts with oxygen, moisture, hydrogen sulfide, sulfurous acid gas in the air to form silver oxide or silver sulfide. Therefore, it has a drawback that the silver surface is discolored (corroded) to brown or black.

As a method of preventing such discoloration (corrosion), (1) silver is added to copper, platinum, palladium, iridium,
It is known to use an alloy with a metal such as zinc or tin, or (2) apply a synthetic resin such as an epoxy resin to the surface.
However, the method (1) has drawbacks such as poor spreadability and poor surface appearance, and the method (2)
There is a drawback that it is difficult to prevent discoloration (corrosion) of the silver surface for a long period of time because of insufficient adhesion to the silver surface or insufficient durability.

[0005]

Therefore, the problem to be solved by the present invention is that silver has sufficient adhesion to the silver surface, which is capable of sufficiently exhibiting the spreadability and beautiful surface appearance that are originally possessed, and There is provided a silver coating resin composition which is excellent in durability such as capable of preventing discoloration (corrosion) of silver.

[0006]

SUMMARY OF THE INVENTION In view of such circumstances, the present inventor has diligently studied and developed a resin composition containing a hydrolyzable silyl group and a radically polymerizable unsaturated double bond. It has been found that it is possible to prevent discoloration (corrosion) of silver, which has excellent adhesiveness to the silver surface and excellent durability, by using and curing with active energy rays, and completed the present invention.

That is, the present invention is characterized by containing a compound having a hydrolyzable silyl group and a radical-polymerizable unsaturated double bond, and is excellent in discoloration (corrosion) resistance to silver and coated with silver. The present invention provides an active energy ray curable resin composition for use.

The present invention comprises 10 to 95% by weight of a saturated compound (A) having a hydrolyzable silyl group and 5 to 90% by weight of an unsaturated compound (B) having a radical-polymerizable unsaturated double bond. , A hydrolyzable silyl group of 0.5 to 2,000
An active energy ray-curable resin composition for silver coating containing mmol / Kg, which further comprises an unsaturated compound (C) having a hydrolyzable silyl group and a radical-polymerizable unsaturated bond in one molecule. Silyl group of 0.5 to 2,000
It also contains an active energy ray-curable resin composition for silver coating containing 0 mmol / Kg.

More specifically, in particular, a saturated compound (A) having a hydrolyzable silyl group, an unsaturated compound (B) having a radical-polymerizable unsaturated double bond, and a hydrolyzable silyl group in one molecule. The active energy ray-curable resin composition for silver coating is characterized in that the unsaturated compound (C) having a radical-polymerizable unsaturated bond is a radical polymer.

These (A), (B) and (C) used in the active energy ray-curable resin composition for silver coating of the present invention.
The radical polymer of each has a weight average molecular weight of 5,
Those of 000 to 800,000 have good adhesion to silver and are particularly preferred.

The present invention also relates to a saturated compound (A) containing a hydrolyzable silyl group and / or an unsaturated compound (C) having a hydrolyzable silyl group and a radical-polymerizable unsaturated bond in one molecule (C) 90- 99.99% by weight and curing catalyst (E)
An active energy ray-curable resin composition for silver coating, which comprises 0.01 to 10% by weight, wherein the unsaturated compound (B) and / or one molecule having a radical-polymerizable unsaturated double bond. Unsaturated compound (C) having a hydrolyzable silyl group and a radical-polymerizable unsaturated bond therein 80 to 99.9
%, And 0.1 to 20% by weight of a photopolymerization initiator (F). An active energy ray-curable resin composition for silver coating is included.

Further, in the present invention, the above-mentioned resin compositions 5 to 9 are used.
It also contains an active energy ray-curable resin composition for silver coating containing 5 wt% to 5 wt% of the acrylic copolymer (D). The present invention will be described in more detail below.

As the hydrolyzable silyl group in the present invention, any hydrolyzable silyl group can be used, and examples thereof include those represented by the general formula (I).

[0014]

Embedded image [Wherein R ₁ represents a hydrogen atom or an organic group selected from an alkyl group or an aralkyl group, R ₂ represents a halogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a phenoxy group, an iminooxy group or an alkenyloxy group. Represent. a represents a natural number of 0, 1 or 2. )

Examples of the hydrolyzable silyl group include a hydroxyl group, a halogen group, an epoxy group, an alkoxy group, an acyloxy group, an amide group, a phenoxy group, an iminooxy group,
Hydroxysilyl group containing a functional group such as an alkenyloxy group, a halosilyl group, an alkoxysilyl group, a phenoxysilyl group, an iminooxysilyl group, an alkenyloxysilyl group and the like, which are easily hydrolyzed, contain a reactive group containing an organic silicon. is there.

Further, for example, trichlorosilyl group, methyldichlorosilyl group, dimethylchlorosilyl group, ethyldichlorosilyl group, diethylchlorosilyl group, methoxydichlorosilyl group, dimethoxychlorosilyl group, trimethoxysilyl group, dimethylmethoxysilyl group. , Methyldimethoxysilyl group, triethoxysilyl group, dimethylethoxysilyl group, methyldiethoxysilyl group, ethoxydichlorosilyl group,

Diethoxychlorosilyl group, diethylmethoxysilyl group, ethyldimethoxysilyl group, diethylethoxysilyl group, ethyldiethoxysilyl group, triacetoxysilyl group, diacetoxymethylsilyl group, dimethylketoxime dimethylsilyl group, ethylmethyl Ketoxime dimethylsilyl group, dimethoxyethylmethylketoxime silyl group, bis (ethylmethylketoxime)
Examples include methoxysilyl group and trisisopropenoxysilyl group.

Examples of the radically polymerizable unsaturated double bond group referred to in the present invention include a (meth) acryloyl group, a vinyl group, a vinyl ether group, a vinyl ester group, an aryl group, a maleimide group and a (meth) acrylamide group.

The active energy ray-curable resin composition for silver coating of the present invention is characterized in that the resin contains a hydrolyzable silyl group and a radical-polymerizable unsaturated double bond. The radical polymerizable unsaturated double bond is
They may be contained in the same compound or may be contained in different compounds.

The hydrolyzable silyl group is contained in the resin composition,
0.5 mmol / Kg to 2,000 mmol / Kg should be contained, and 1 mmol / Kg to 500 mmol /
Kg is particularly preferred. If the amount is less than 0.5 mmol / Kg, the adhesion to silver is insufficient and the amount is 2,000 mm.
If it is more than ol / Kg, the stability becomes poor.

The active energy ray-curable resin composition for silver coating containing a hydrolyzable silyl group and a radically polymerizable unsaturated double bond of the present invention is a saturated compound (A) having a hydrolyzable silyl group and a radical. The unsaturated compound (B) having a polymerizable unsaturated double bond and / or the unsaturated compound (C) having a hydrolyzable silyl group and a radical polymerizable unsaturated bond in one molecule are used as essential components for hydrolysis. Acrylic copolymer (D) which does not have a polymerizable silyl group and a radical-polymerizable unsaturated double bond, a curing catalyst (E), and a photopolymerization initiator (F) are contained as necessary.

An active energy ray-curable resin composition for silver coating prepared by blending a saturated compound (A) having a hydrolyzable silyl group and an unsaturated compound (B) having a radical-polymerizable unsaturated double bond. , (A) :( B) = 10-95% by weight: 5-90% by weight is preferable. When the content of the saturated compound (A) having a hydrolyzable silyl group is less than 10% by weight, the adhesion to silver is insufficient, and the unsaturated compound (B) having a radical polymerizable unsaturated double bond Is 5
If it is less than wt%, the effect of preventing discoloration (corrosion) of the silver surface is poor.

The unsaturated compound (C) having a hydrolyzable silyl group and a radically polymerizable unsaturated bond in one molecule may be used alone as an active energy ray-curable resin composition for silver coating, You may use together with said (A) and (B).

Examples of the saturated compound (A) having a hydrolyzable silyl group include a silane coupling agent (A1), an oligomerization product of an alkoxysilyl compound (A2) and a compound (A) obtained by grafting a hydrolyzable silyl group onto a saturated compound.
3) etc. As the silane coupling agent (A1),
Some have a hydrolyzable silyl group and a mercapto group, an epoxy group, an amino group, a chloro group, an isocyanate group and the like in the same molecule.

Typical examples of the mercapto group-containing silane coupling agent (A11) are γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane and γ-mercaptopropyltrimethoxysilane. Isopropenyloxysilane, γ-mercaptopropyltriiminooxysilane, mercaptomethyldimethoxysilane, mercaptomethyldiethoxysilane, mercaptomethylethyldimethoxysilane,

Mercaptomethylethyldiethoxysilane, 2-mercaptoethylmethyldimethoxysilane, 2
-Mercaptoethylmethyldiethoxysilane, 2-mercaptoethylethyldimethoxysilane, 2-mercaptoethylethyldiethoxysilane, 4-mercaptobutylmethyldimethoxysilane, 4-mercaptobutylmethyldiethoxysilane, 4-mercaptobutylethyldimethoxysilane, 4-mercaptobutylethyldiethoxysilane and the like.

Epoxy group-containing silane coupling agent (A
Typical examples of 12) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane. , Γ-glycidoxypropyltriisopropenyloxysilane, γ-glycidoxypropyltriiminooxysilane,

Isocyanate group-containing γ-isocyanatopropyltriisopropenyloxysilane or γ-isocyanatopropyltrimethoxysilane Adduct of silane coupling agent with glycidol, primary amino group-containing γ-aminopropyltrimethoxysilane or the like Adduct of silane coupling agent and diepoxy compound, β- (3,
4 epoxycyclohexyl) ethyltrimethoxysilane and the like.

Amino group-containing silane coupling agent (A1
Typical examples of 3) include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane and N- (β-aminoethyl ) -Γ-aminopropylmethyldimethoxysilane, aminoethylaminomethylphenylethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and the like.

Chloro group-containing silane coupling agent (A1
Typical examples of 4) include γ-chloropropyltrimethoxysilane and γ-chloropropylmethyldimethoxysilane. Typical examples of the isocyanate group-containing silane coupling agent (A15) include 3-isocyanatopropyltriethoxysilane.

The oligomerization product (A2) of an alkoxysilyl compound means, as an alkoxysilyl compound, tetraalkoxysilane such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc., which is acidic, neutral or basic. Water is added by a necessary amount to remove alcohol generated by the reaction (a double mole of added water is generated), and the hydrolysis rate is 0 to 65%, preferably the hydrolysis rate is 10 to 10. 60%, particularly preferably 40-60%
The silicate oligomer of is good.

The resin (A3) grafted with a hydrolyzable silyl group is a compound (A31) obtained by reacting a silane coupling agent with a saturated compound having a functional group that reacts with the functional group of the silane coupling agent. ), A compound (A32) obtained by reacting a silicon hydride compound and a compound having an olefin group, and a radical polymer obtained by radical copolymerizing a silane coupling agent and a radically polymerizable double bond-containing unsaturated compound. (A33) etc.

In the compound (A31) obtained by reacting a silane coupling agent with a saturated compound having a functional group that reacts with the functional group of the silane coupling agent, the functional group of the silane coupling agent and the saturated compound have Examples of the combination of functional groups include, for example, a combination of mercapto group / radical polymerizable group (the same applies hereinafter),

Amino group / radical polymerizable group, hydroxyl group / isocyanate group, mercapto group / isocyanate group, amino group / isocyanate group, carboxyl group / epoxy group, carboxyl group / hydroxyl group, carboxyl group / amino group, acid anhydride group / There are hydroxyl group, acid anhydride group / amino group, hydroxyl group / epoxy group, amino group / epoxy group and the like.

The above-mentioned ones are not limited to the functional groups of the silane coupling agent, but may be the functional groups of the saturated compound. For example, a resin obtained by reacting a mercapto group-containing resin with a radical-polymerizable double bond group-containing silane coupling agent (A16), a radical-polymerizable double bond group-containing resin, and a mercapto group-containing silane coupling agent (A11) Resin reacted with a hydroxyl group-containing resin, a resin obtained by reacting an isocyanate group-containing silane coupling agent (A15), a resin obtained by reacting an isocyanate group-containing resin with an amino group-containing silane coupling agent (A13), a carboxyl group Examples of the group-containing resin include a resin obtained by adding an epoxy group-containing silane coupling agent (A12).

Typical examples of the radical-polymerizable double bond group-containing silane coupling agent (A16) include γ- (meth) acryloyloxypropyltrimethoxysilane,
γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, γ- (meth) acryloyloxypropyltripropenyloxysilane,

Γ- (meth) acryloyloxypropyltriiminooxysilane, vinyltrimethoxysilane,
Vinyltriethoxysilane, vinyl (tris-β-methoxyethoxy) silane, vinyltriacetoxysilane,
Examples thereof include vinyltrichlorosilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride.

In the compound (A32) obtained by reacting the silicon hydride compound (A32-1) with the compound (A32-2) having an olefin group, the silicon hydride compound (A32-1) is trichlorosilane, Halogenated silanes such as methyldichlorosilane, dimethylchlorosilane, trimethylsiloxydichlorosilane, trimethoxysilane, triethoxysilane, methyldimethoxysilane, phenyldimethoxysilane,

Alkoxysilanes such as 1,3,3,5,5,5,7,7-heptamethyl-1,1-dimethoxytetrasiloxane, acyloxysilanes such as methyldiacetoxysilane and trimethylsiloxymethylacetoxysilane, and bis. (Dimethyl ketoximate) methylsilane,
Bis (cyclohexyl ketoximate) methylsilane,

Ketoximates such as bis (diethyl ketoximate) trimethylsiloxysilane, dimethylsilane, trimethylsiloxymethylsilane, hydrosilanes such as 1,1-dimethyl-2,2-dimethyldicycloxane, methyltri (isopropenyl). (Oxy) silane and the like alkenyloxysilanes.

In the compound (A32-2) having an olefin group, examples of the olefin group include those represented by the general formula (II).

General formula (II)

CH ₂ ═CH (R ₁ ) —R ₂ — (In the formula, R ₁ is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and R ₂ is the same or different carbon number 1 to 1 20 divalent organic groups are shown)

As the compound (A32-2) having an olefin group, for example, when an epoxy compound such as ethylene oxide or propylene oxide is polymerized, an olefin group-containing epoxy compound such as allyl glycidyl ether is added for copolymerization. There are things to synthesize by things.

The reaction between the silicon hydride compound (A32-1) and the compound having an olefin group (A32-2) is carried out using platinum black,
When a platinum compound such as chloroplatinic acid, a platinum alcohol compound, a platinum olefin complex, a platinum aldehyde complex or a platinum ketone complex is used as a catalyst, a resin having a hydrolyzable silyl group grafted can be obtained.

Radical Polymerizable with Silane Coupling Agent 2
The radical polymer (A33) obtained by radically copolymerizing a heavy bond-containing unsaturated compound includes radically polymerizable 2
A silane coupling agent containing a heavy bond group (A16) and / or a silane coupling agent containing a mercapto group (A11),
There is a radical polymer obtained by radically copolymerizing a radically polymerizable double bond-containing unsaturated compound (A33-1).

As the radically polymerizable double bond-containing unsaturated compound (A33-1), methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,
Butyl (meth) acrylate, allyl (meth) acrylate, phenyl (meth) acrylate, pentyl (meth) acrylate, lauryl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate,
Cyclohexyl (meth) acrylate, isobornyl acrylate (meth), vinyl (meth) acrylate,

Hydroxyl radicals such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, N-methylol (meth) acrylamide and (meth) aryl alcohol. Polymerizable double bond-containing unsaturated compounds, carboxyl group-containing vinyl monomers such as (meth) acrylic acid, maleic acid, itaconic acid, fumaric acid and crotonic acid, maleic anhydride,

Acid anhydride group-containing vinyl monomers such as itaconic anhydride, sulfonic acid group-containing vinyl monomers such as p-styrenesulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid, (meth) acrylic Aminoethyl acid, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, β-aminoethyl vinyl ether, dimethylaminoethyl vinyl ether, vinylamine,

Vinylmethylamine, vinylethylamine, vinyldimethylamine, vinyldiethylamine,
(Meth) allylamine, (meth) allyldimethylamine, (meth) allyldiethylamine, vinyldiphenylamine, amino group-containing vinyl monomers such as p-aminostyrene, vinyl acetate, various vinyl esters such as vinyl benzoate, styrene , Aromatic vinyl monomers such as α-methylstyrene and ο-methylstyrene, vinyl cyanide monomers such as (meth) acrylonitrile,

Ethylenically unsaturated ether type monomers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, methyl allyl ether and ethyl allyl ether, Cilaplane FM0711 (molecular weight of 1,00)
0), the same FM0721 (molecular weight 5,000), the same FM0
725 (molecular weight 10,000) and the like, methacryloxypropyl dimethyl polysiloxane with one terminal, fluorine-containing vinyl monomers and the like.

One of these copolymerizable vinyl monomers may be used alone, or two or more thereof may be mixed and used. It is preferable to use an unsaturated compound containing one radically polymerizable double bond, but an unsaturated compound containing two or more radical polymerizable double bonds may be used.

In the copolymerization, it is preferable to use an organic acid having 8 or more carbon atoms in an amount of 0.1 to 5% by weight of the polymerization mixture. The polymerization catalyst is 0.1 to 3% by weight, preferably 0.2 to 2% by weight, based on the total amount of all unsaturated compounds.
It is advisable to use a radical polymerization initiator of, for example, benzoyl peroxide, azobisisobutyronitrile or the like.

Polymerization can be carried out by either bulk polymerization or solution polymerization, but solution polymerization is easier to use in the compounding step. The solvent includes alcohols, and specific examples thereof include methanol, ethanol, isopropanol,
Examples include n-butanol and isoamyl alcohol. In addition, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, and ketones such as acetone and methyl ethyl ketone may be used alone or in combination. The polymerization conditions (temperature, time) are not particularly limited, but usually 50 to 150 ° C. and the reaction is completed in 2 to 10 hours.

As the unsaturated compound (B) having a radical-polymerizable unsaturated double bond, there are a prepolymer (B1) having a radical-polymerizable property and a monomer (B2) having a radical-polymerizable property. Examples of the radical-polymerizable prepolymer (B1) include urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, polybutadiene (meth) acrylate having a molecular weight of 500 or more.

(Meth) acryl compounds such as silicone (meth) acrylate, polyether (meth) acrylate, melamine (meth) acrylate, phosphazene (meth) acrylate, and acrylic copolymer having (meth) acryloyl group introduced thereinto; Compounds having unsaturated bonds in the main chain and side chains such as polybutadiene and unsaturated polyester compounds; allyl group, vinyl group, vinyl ether group,
A compound having a radically polymerizable double bond such as a maleimide group or a (meth) acrylamide group;

Examples thereof include compounds that cause a radical addition reaction such as thiol compounds and amino compounds. These may be appropriately selected and used so as to satisfy the required physical properties, and usually those having a molecular weight of about 500 to 30,000 are used alone or as a mixture.

The radical-polymerizable monomer (B2) may be a compound having a molecular weight of less than 500 and capable of radical polymerization or radical addition reaction in a bulk or liquid state, such as a (meth) acrylic compound, Examples thereof include saturated polyester compounds, vinyl compounds, vinyl ether compounds, maleimide compounds, (meth) acrylamide compounds, thiol compounds and amino compounds.

Among them, the (meth) acrylic compound, the (meth) acrylamide compound and the vinyl ether compound are
It is preferable because it has high reactivity. Specific examples of the radically polymerizable monomer (B2) include (meth) acrylamide, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and hexyl (meth) acrylate. Two
-Ethylhexyl (meth) acrylate, dodecyl (meth) acrylate,

Lauryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) ) Acrylate, isobornyl (meth) acrylate, N-methylmaleimide, N-phenylmaleimide, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,

Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
1,6-hexanedi (meth) acrylate, bisphenol A dioxydiethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,4-butanediol di (meth) acrylate,
Examples include N-vinylpyrrolidone and tripropylene glycol divinyl ether.

As the unsaturated compound (B) having a radical polymerizable unsaturated double bond, it is preferable to use a compound having two or more radical polymerizable unsaturated double bonds. When only a compound having one radical-polymerizable unsaturated double bond is used, discoloration (corrosion) resistance is not improved.

Particularly, polyfunctional (meth) acrylate compounds having a cyclic structure are particularly effective. Examples of the cyclic structure include a benzene ring, a cyclohexane ring, a dicyclopentane ring, a dicyclopentene ring, a tricyclodecane ring, a naphthalene ring, a fluorene ring, a triazine ring,
1,3-dioxolane ring, 1,3-dioxane ring, 1,
There is a 4-dioxane ring and the like.

As the polyfunctional (meth) acrylate compound having a cyclic structure, SR-349 manufactured by Sartomer Co., USA,
Kayarad R550, R551 and 71 manufactured by Nippon Kayaku Co., Ltd.
2, the same HBA-024E, the same HBA-240P, NK ester A-BPE-10, the same A-BPP manufactured by Shin Nakamura Chemical Co., Ltd.
-3, bisphenol A such as light ester BP-2PA and BP-4PA manufactured by Kyoeisha Chemical Co., Ltd., Aronix M205 manufactured by Toagosei Co., Ltd., and di (meth) acrylate of alkylene oxide modified bisphenol compounds such as S, and

Di (meth) acrylate of hydrogenated bisphenol, di (meth) acrylate of modified alkylene oxide of hydrogenated bisphenol, di (meth) acrylate of modified alkylene oxide of trisphenol. Trisphenol-based di (meth) acrylates such as hydrogenated trisphenol di (meth) acrylate, hydrogenated trisphenol alkylene oxide-modified di (meth) acrylate, and the like,

Di (meth) acrylate of alkylene oxide modified product of p, p'-biphenol, hydrogenated p,
Biphenol di (meth) acrylates such as di (meth) acrylates of p'-biphenols and alkylene oxide modified products of hydrogenated biphenols, and alkylene oxide modifications of p, p'-dihydroxybenzophenones Dihydroxybenzophenone-based di (meth) acrylates such as body di (meth) acrylate,

Aronix M6100, M manufactured by Toagosei Co., Ltd.
6250, M6200, M6500, M8100, M8
Phthalate di (meth) acrylates such as 030, M8060, M7100 and Kayarad R684 manufactured by Nippon Kayaku Co., Ltd.
Dicyclopentane-based di (meth) acrylates such as Aronix M215, M315, M325 manufactured by Toagosei Co., Ltd.
And other isocyanurate-based di (meth) acrylates.

Examples of the unsaturated compound (C) having a hydrolyzable silyl group and a radical-polymerizable unsaturated bond include:
Radical-polymerizable double bond group-containing silane coupling agent (A16) and unsaturated compounds having a functional group that reacts with the silane coupling agent and the functional groups of the silane coupling agent (C
There are compounds (C1) and the like obtained by reacting 11).

In the compound (C1) obtained by reacting a silane coupling agent and an unsaturated compound having a functional group that reacts with the functional group of the silane coupling agent, in the compound (C1), the functional group of the silane coupling agent and the unsaturated compound ( Examples of the combination of functional groups possessed by C11) include a combination of mercapto group / radical polymerizable group (the same applies hereinafter), amino group / radical polymerizable group, hydroxyl group / isocyanate group, mercapto group / isocyanate group, amino group / isocyanate. Group, carboxyl group / epoxy group, carboxyl group / hydroxyl group, carboxyl group / amino group, acid anhydride group / hydroxyl group, acid anhydride group / amino group, hydroxyl group / epoxy group, amino group / epoxy group and the like.

The above-mentioned functional group is not limited to the functional group of the silane coupling agent, and may be the functional group of the unsaturated compound. For example, (1); a compound obtained by reacting a hydroxyl group-containing radically polymerizable unsaturated compound (C11-1) with an isocyanate group-containing silane coupling agent (A15).

As the hydroxyl group-containing radically polymerizable unsaturated compound (C11-1), acryloyl compound having a hydroxyl group, methacryloyl compound having a hydroxyl group, allyl compound having a hydroxyl group, vinyl ether compound having a hydroxyl group, vinyl compound having a hydroxyl group, hydroxyl group And an acrylamide compound having a hydroxyl group and a maleimide compound having a hydroxyl group.

Specific examples of the acryloyl compound having a hydroxyl group and the methacryloyl compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate,
4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2
-Hydroxypropyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate,

2-hydroxyethyl (meth) acrylate modified with caprolactone, phthalic acid (meth) acrylate modified with ethylene oxide, 3- (meth) acryloyloxyglycerin monomethacrylate, pentaerythritol tri (meth) acrylate, bis {(meth) acryloxy. Ethyl} hydroxyethyl isocyanurate,
Trimethylolpropane di (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, etc.

Examples of the allyl compound having a hydroxyl group include pentaerythritol triallyl ether, trimethylolpropane diallyl ether, 2-propen-1-ol, and 4-hydroxybutylallyl ether. Vinyl ether, butanediol monovinyl ether, cyclohexanedimethanol monovinyl ether, diethylene glycol monovinyl ether, hexanediol monovinyl ether, etc.

Examples of the vinyl compound having a hydroxyl group include both-terminal alcoholic polyisoprene TL-20 (manufactured by Kuraray Co., Ltd.) and both-terminal alcoholic polybutadiene R-15.
HT, R-45HT (manufactured by Idemitsu Petrochemical Co., Ltd.), etc.,
Esterification of unsaturated group-containing polycarboxylic acids such as linoleic acid, linolenic acid, maleic anhydride, maleic acid, fumaric acid, itaconic acid and tetrahydrophthalic anhydride with polyhydric alcohols such as 1,6-hexanediol Unsaturated polyesters having alcohol groups at both terminals or one terminal obtained by, for example, cinnamyl alcohol and the like, and also as a (meth) acrylamide compound having a hydroxyl group,
Examples include N-methylol (meth) acrylamide.

(2); 2 for compounds having 2 or more hydroxyl groups
The above-mentioned compound having an isocyanate group is reacted, and this isocyanate group-containing reaction product is combined with a compound having an active hydrogen group such as a hydroxyl group, a mercapto group and an amino group and a radical-polymerizable double bond in one molecule, and a mercapto compound. A compound having an active hydrogen group and a hydrolyzable silyl group in one molecule such as a group-containing silane coupling agent (A11) and an amino group-containing silane coupling agent (A13) is mixed in a desired mixing ratio (90:10).
Compounds obtained by reacting at a ratio of 10 to 90).

(3); 2 for compounds having 2 or more hydroxyl groups
An isocyanate group-containing reaction product obtained by reacting the above-mentioned compound having an isocyanate group with an active hydrogen group such as a hydroxyl group, a mercapto group and an amino group, a radically polymerizable double bond and a hydrolyzable silyl group in one molecule. Compound with a group (C
Compounds obtained by reacting 11-2).

The compound (C11-2) having an active hydrogen group such as a hydroxyl group, a mercapto group, an amino group, a radical-polymerizable double bond and a hydrolyzable silyl group in one molecule is (meth) acrylic acid or the like. In addition to the carboxyl group-containing radically polymerizable unsaturated compound of (3), an epoxy group-containing silane coupling agent such as γ-glycidoxypropyltrimethoxysilane (A
12) reacted,

An epoxy group-containing unsaturated compound such as glycidyl (meth) acrylate is reacted with an amino group-containing silane coupling agent (A13) such as γ-aminopropyltrimethoxysilane or a mercapto group-containing silane coupling agent (A11). Examples of such compounds include those prepared by reacting two or more hydroxyl group-containing radically polymerizable unsaturated compounds with an isocyanate group-containing silane coupling agent (A15) such as isocyanatopropyltrimethoxysilane.

(4): Polyisocyanate compound (C11
-3), an amino group-containing silane coupling agent (A13),
A silane coupling agent containing an active hydrogen group such as a mercapto group-containing silane coupling agent (A11) and an epoxy group-containing silane coupling agent (A12) is used as an isocyanate group containing 50
-90% addition reaction, and the remaining isocyanate group is reacted with a hydroxyl group-containing radically polymerizable unsaturated compound (C11-1).

Examples of the polyisocyanate compound (C11-3) include trimethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3
-Cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate),

Methyl 2,4-cyclohexane diisocyanate, methyl 2,6-cyclohexane diisocyanate, 1,4-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, m-phenylene diisocyanate, p-phenylene diisocyanate , 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate,

4,4'-diphenylmethane diisocyanate (MDI), 2,4- or 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, dianidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 1,3 -Or 1,4-
Xylylene diisocyanate, ω, ω′-diisocyanate-1,4-diethylbenzene, 1,3-bis (α,
α-dimethylisocyanate methyl) benzene, m-xylene diisocyanate,

Lysine diisocyanate methyl ester,
Isophorone diisocyanate, triphenylmethane triisocyanate, tris (4-phenylisocyanate) thiophosphate, 2,4-tolylene diisocyanate trimethylol propane adduct, hexamethylene diisocyanate-trimethylol propane adduct, 2,4-tolylene diisocyanate 2 A quantity,

Hexamethylene diisocyanate trimer,
2,4-Tolylene diisocyanate trimer, 2,4-Tolylene diisocyanate (3 mol) -hexamethylene diisocyanate (2 mol) copolymer, hexamethylene diisocyanate (3 mol) -water (1 mol) copolymer and so on.

As the acrylic copolymer (D), known and commonly used acrylic copolymers can be used without particular limitation. In the active energy ray-curable resin composition for silver coating of the present invention, other liquid or solid oligomers or resins having low or no radical reactivity can be used together. These include, for example, liquid polybutadiene, liquid polybutadiene derivatives, liquid chloroprene, liquid polypentadiene, dicyclopentadiene derivatives, saturated polyester oligomers, polyether oligomers, liquid polyamides,

Cellulose derivatives such as polyisocyanate oligomer, xylene resin, ketone resin, petroleum resin, fluorine-based oligomer / resin, silicon-based oligomer / resin, polysulfide-based oligomer / resin, nitrocellulose, benzyl cellulose, acetyl cellulose, acetyl butyl cellulose, etc. , Vinyl chloride / vinyl acetate copolymer resin, other vinyl chloride copolymer resin, vinylidene chloride or its copolymer resin, rack or copearl resin, fatty acid modified urethane resin, lacquer,

Oxidation-polymerized resin resins such as oil-modified phenolic resins, alkyd resins, amino-alkyd resins, epoxy resins / fatty acid esters, epoxy resins, polyurethane resins, acrylic resins, acrylic resins / polyurethanes,
Vinyl resin etc. These non-reactive oligomers and resins may have functional groups such as halogen, epoxy group, amino group, hydroxyl group, thiol group, amide group, carboxyl group, phosphoric acid group and sulfonic acid group.

The curing catalyst (E) used as required includes basic compounds such as lithium hydroxide and potassium hydroxide, lead-2-ethyl octate, dibutyltin diacetate, dibutyltin dilaurylate, butyltin tri-. 2-ethylhexoate, stannous caprylate, tin naphthenate, tin oleate, tin butyrate, tin octylate, iron-2-ethylhexanoate, cobalt-2
-Ethyl hexoate, cobalt-2-ethyl tin naphthenate, cobalt naphthenate,

Metal salts of carboxylic acids such as manganese-2-ethylhexanoate, zinc-2-ethylhexoate, zinc stearate, zinc naphthenate and zinc stearate, tetrabutyl titanate and tetra-2-ethylhexyl. Titanate, triethanolamine titanate,
Organic titanate esters such as tetra (isopropenyloxy) titanate, organosiloxane titanium and β-
Organic titanium compounds such as carbonyl titanium,

Alkoxyaluminum compounds, quaternary ammonium salts such as benzyltriethylammonium acetate, lower fatty acid salts of alkali metals such as potassium acetate, sodium acetate and lithium bromide, dialkylhydroxyamines such as dimethylhydroxyamine and diethylhydroxyamine. , P-toluenesulfonic acid, acidic compounds such as dialkylphosphoric acid, and the like.

The amount of the curing catalyst (E) added is such that the saturated compound (A) having a hydrolyzable silyl group and / or the unsaturated compound having a hydrolyzable silyl group and a radical-polymerizable unsaturated bond in one molecule. Usually, 0.01 to 10 is relative to 90 to 99.99% by weight of the resin composition comprising the compound (C).
Wt% is added. Particularly, 0.1 to 5% by weight is preferable.
If it is more than 10% by weight, the stability of the resin composition upon leaving is deteriorated, and if it is 0.01% by weight or less, the catalytic effect is not sufficiently obtained.

When ultraviolet rays are used as a curing means for the resin composition of the present invention, it is usually necessary to add (F) a photopolymerization initiator to the resin composition. The amount of the photopolymerization initiator added is an unsaturated compound (B) having a radical polymerizable unsaturated double bond and / or an unsaturated compound (C) having a hydrolyzable silyl group and a radical polymerizable unsaturated bond. The resin composition is usually used in an amount of 0.
1 to 20% by weight, preferably 0.5 to 10% by weight
Is. If the amount is more than 20% by weight, the ultraviolet rays are prevented from passing through the inside of the coating film, resulting in insufficient curing.

The photopolymerization initiator can be roughly classified into two types, that is, a bond which is cleaved in the molecule by light to produce an active species and a photopolymerization initiator which produces an active species by causing a hydrogen abstraction reaction between molecules. Examples of the former include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1- (4-
Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one,

4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-
2-morpholino (4-thiomethylphenyl) propane-
1-one, 2-benzyl-2-dimethylamino-1-
Acetophenone type such as (4-morpholinophenyl) -butanone; Benzoin type such as benzoin, benzoin isopropyl ether, benzoin isobutyl ether;
Acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; benzyl, methylphenylglyoxyester, etc.,

Examples of the latter include benzophenone, ο-
Methyl benzoylbenzoate, 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, acrylated benzophenone, 3,
Benzophenone compounds such as 3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and 3,3'-dimethyl-4-methoxybenzophenone;

2-isopropylthioxanthone, 2,4
Thioxanthones such as dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; aminobenzophenones such as Michler's ketone and 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethyl Examples include anthraquinone, 9,10-phenanthrenequinone and camphorquinone.

When the resin composition of the present invention is irradiated with ultraviolet rays, it is cured only by adding the above-mentioned photopolymerization initiator, but it is preferable to use a photosensitizer together in order to further improve the curability. Examples of such photosensitizers include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and benzoic acid (2-dimethyl Amino) ethyl,

Examples of amines include (n-butoxy) ethyl 4-dimethylaminobenzoate and 2-ethylhexyl 4-dimethylaminobenzoate. The blending amount of the photosensitizer is an unsaturated compound (B) having a radical polymerizable unsaturated double bond and / or an unsaturated compound (C) having a hydrolyzable silyl group and a radical polymerizable unsaturated bond. The resin composition is usually contained in an amount of 0.01 to 100% by weight based on 80 to 99.9% by weight.
It is 20% by weight, preferably 0.05 to 10% by weight.
If the amount is more than 20% by weight, the ultraviolet rays are prevented from passing through the inside of the coating film, resulting in insufficient curing.

The active energy ray-curable resin composition for silver coating of the present invention comprises a saturated compound (A) having a hydrolyzable silyl group and an unsaturated compound (B) having a radical-polymerizable unsaturated double bond, or An unsaturated compound (C) having a hydrolyzable silyl group and a radically polymerizable unsaturated bond is used as an essential component, and an acrylic polymer (D), a curing catalyst (E), and a photopolymerization initiator (F) are added as necessary. , Contained.

When the active energy ray-curable resin composition for silver coating of the present invention contains a radical polymer, particularly an acrylic polymer, the adhesion to silver and the resistance to discoloration (corrosion) with respect to silver are dramatically improved. improves. Therefore, as a method of incorporating the radical polymer into the resin composition, the saturated compound (A) having a hydrolyzable silyl group is a radical polymer, particularly an acrylic polymer, and a radical polymerizable unsaturated double The unsaturated compound (B) having a bond is a radical polymer, particularly an acrylic polymer,

The unsaturated compound (C) having a hydrolyzable silyl group and a radical-polymerizable unsaturated double bond is a radical polymer, particularly an acrylic polymer, and also contains an acrylic polymer (D). . Both methods are effective, but in particular, the saturated compound (A) having a hydrolyzable silyl group is an acrylic polymer, and the unsaturated compound having a hydrolyzable silyl group and a radical-polymerizable unsaturated double bond The fact that (C) is an acrylic polymer is effective in improving the adhesion to silver.

In any case, these (A) to (D)
The weight average molecular weight of the radical polymer is 5,000 to 8
It is preferably 0,000. If it is less than 5,000, the adhesion to silver becomes insufficient, and 800,000 is obtained.
If it is larger, the coatability will be poor and the smoothness of the coated surface will be insufficient.

The radical polymer having a hydrolyzable silyl group is obtained by reacting a radical polymer having a functional group (A34-1) with a silane coupling agent (A34), a silane coupling agent and a radical polymerizable compound. Radical polymer obtained by radically copolymerizing a double bond-containing unsaturated compound (A
33) etc.

The combination with the functional group of the silane coupling agent that reacts with the functional group of the radical polymer is such that when a saturated compound having a functional group is reacted with the silane coupling agent to prepare a compound (A31). You can refer to the combination.

Radical polymer having functional group (A34-1)
Is a radical polymer (A33) prepared by radically copolymerizing a silane coupling agent and a radically polymerizable double bond-containing unsaturated compound. A radical having a functional group is used instead of the silane coupling agent. An unsaturated compound containing a polymerizable double bond may be used. The radical-polymerizable double bond-containing unsaturated compound having a functional group may be appropriately selected from the radical-polymerizable double bond-containing unsaturated compound (A33-1) described in the method for preparing the radical polymer (A33).

The radical copolymer (B3) having a radical-polymerizable unsaturated double bond is a compound (B31- having a radical-polymerizable unsaturated double bond in the radical polymer (B31-1) having a functional group. 2) is reacted with (B31) and an unsaturated compound (B32-1) having two or more kinds of unsaturated double bonds having different radical polymerizability is radically polymerized to have a radically reactive group having slow reactivity. There are radical copolymers (B32) and the like.

The combination with the functional group of the compound (B31-2) having a radical-polymerizable unsaturated double bond, which is reacted with the functional group of the radical polymer (B31-1), is a combination of a saturated compound having a functional group and a silane. The combination used in producing the compound (A31) obtained by reacting the coupling agent may be referred to.

Examples of the compound (B31-2) having a radical-polymerizable unsaturated double bond which is reacted with the functional group of the radical polymer include unsaturated compounds having an epoxy group such as glycidyl (meth) acrylate and 2-isocyanate. Unsaturated compounds having isocyanate groups such as natoethyl (meth) acrylate, unsaturated compounds having organic acid groups such as (meth) acrylic acid, unsaturated compounds having hydroxyl groups such as β-hydroxypropyl (meth) acrylate Examples include compounds, unsaturated compounds having an aziridinyl group such as 2- (1-aziridinyl) ethyl (meth) acrylate, unsaturated compounds having an anhydride group such as anhydrous (meth) acrylic acid, and the like.

Further, after reacting a compound having an anhydride group such as maleic anhydride or phthalic anhydride with the functional group of the radical polymer, a compound having a radical polymerizable unsaturated double bond is reacted. You may let me. The radical polymer (B31-1) having a functional group is prepared by the same method as the radical polymer (A33) obtained by radical copolymerizing a silane coupling agent and a radically polymerizable double bond-containing unsaturated compound. Instead of the coupling agent, a radical-polymerizable double bond-containing unsaturated compound having a functional group may be used.

The radical-polymerizable double bond-containing unsaturated compound having a functional group can be appropriately selected from the radical-polymerizable double bond-containing unsaturated compound (A33-1) described in the method for preparing the radical polymer (A33). Good. Unsaturated compounds having two or more kinds of unsaturated double bonds with different radical polymerizability (B32-
In 1), the unsaturated double bond having different radical polymerizability is, for example, appropriately selected from the group consisting of an acrylic group, a methacrylic group, an aryl group, a vinyl group, an intramolecular double bond and the like.
You can choose more than one species.

Examples of the unsaturated compound (B32-1) having two or more kinds of unsaturated double bonds having different radical polymerizable properties are dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ( (Meth) vinyl acrylate and the like. An unsaturated compound (B32-1) having two or more kinds of unsaturated double bonds having different radical polymerizable properties,
A radical copolymer (B32) having a radical-polymerizable unsaturated double bond can be obtained by using the same method as the radical polymer (A33) in place of the silane coupling agent.

The radical copolymer (C2) having a hydrolyzable silyl group and a radical-polymerizable unsaturated double bond is, for example, a radical copolymer having neither a hydrolyzable silyl group nor a radical-polymerizable unsaturated double bond. A compound obtained by reacting a compound having a hydrolyzable silyl group such as a silane coupling agent with an unsaturated compound having a radically polymerizable unsaturated double bond, a radical copolymer having a hydrolyzable silyl group,
A reaction product of an unsaturated compound having a radical-polymerizable unsaturated double bond,

There is a radical copolymer having a radically polymerizable unsaturated double bond, which is obtained by reacting a compound having a hydrolyzable silyl group such as a silane coupling agent. The method of reacting the compound having a hydrolyzable silyl group such as a silane coupling agent with the radical copolymer may be the same as the method of producing the resin (A3) grafted with the hydrolyzable silyl group.

A method of reacting a radical copolymer with an unsaturated compound having a radical-polymerizable unsaturated double bond is as follows:
The method for producing the unsaturated compound (C) having a hydrolyzable silyl group and a radical polymerizable unsaturated bond may be the same as the method for reacting an unsaturated compound having a radical polymerizable unsaturated bond. The radical copolymer can be obtained by a method similar to that of the radical polymer (A33) and appropriately selecting and polymerizing a radical copolymer having an effective radical polymerizable unsaturated double bond.

An acrylic copolymer (D) having no hydrolyzable silyl group and a radical-polymerizable unsaturated double bond is prepared in the same manner as the radical polymer (A33), in place of the silane coupling agent. A radical-polymerizable double bond-containing unsaturated compound containing no hydrolyzable silyl group may be used.

In the resin composition of the present invention, in addition to the above-mentioned components, known pigments, dyes, inorganic fillers, organic fillers, and commonly used pigments are used within a range not impairing the silver coating property which is a unique effect of the present invention. Matting agent, antifoaming agent, leveling agent, wetting / dispersing agent,
Anti-settling agent, thickening agent / anti-sagging agent, anti-color separation agent, emulsifier, anti-slip / scratch agent, plasticizer, adhesion improver for coupling, anti-skin agent, drying agent, UV absorber (light stability Agent), antioxidant, polymerization inhibitor, heat stabilizer,
Antibacterial / antifungal agents, flame retardants, antifouling agents, antistatic agents, conductive agents (electrostatic assistants), etc. may be added.

Furthermore, in applications such as paints and coating agents,
If necessary, an organic solvent or water may be added to adjust the viscosity, but in this case, it is preferable to remove the organic solvent or water before the curing with active energy rays. As the pigment or dye, an oil-degradable dye is suitable because of its excellent solubility, but any pigment or dye may be used. In addition, known and commonly used inorganic fillers and organic fillers may be used for improving mechanical properties such as strength, cushioning property and slipperiness.

As the inorganic filler, silicon dioxide, silicon oxide, calcium carbonate, calcium silicate, magnesium carbonate, magnesium oxide, talc, kaolin clay, calcined clay, zinc oxide, zinc sulfate, aluminum hydroxide, aluminum oxide, glass, Examples include mica, barium sulfate, alumina white, zeolite, silica balloons, glass balloons.

A halogen group, an epoxy group, an amino group, a silane coupling agent, a titanate-based coupling agent, an aluminum-based coupling agent, a zirconate-based coupling agent, etc. are added to the inorganic filler and reacted. It may have a functional group such as a hydroxyl group, a thiol group, an amide group, a carboxyl group, a phosphoric acid group and a sulfonic acid group.

As the organic filler, benzoguanamine resin, melamine resin, benzoguanamine / melamine resin,
Urea resin, silicone resin, low density polyethylene, high density polyethylene, polyolefin resin, ethylene / acrylic acid copolymer, polystyrene, crosslinked polystyrene, polydivinylbenzene, styrene / divinylbenzene copolymer, acrylic copolymer, crosslinked acrylic resin ,

Polymethylmethacrylate resin, vinylidene chloride resin, fluororesin, nylon 12, nylon 1
1, nylon 6/66, phenol resin, epoxy resin, urethane resin, polyimide resin and the like. The organic filler may have a functional group such as a halogen group, an epoxy group, an amino group, a hydroxyl group, a thiol group, an amide group, a carboxyl group, a phosphoric acid group and a sulfonic acid group.

As the coupling agent, tetra (2,2
-Diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyldimethacrylisostearoyl titanate, isopropyldiacrylisostearoyl titanate, isopropyltriisostearoyl titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl) Pyrophosphate) ethylene titanate,

Titanate coupling agents such as isopropyl tridodecylbenzene sulfonyl titanate and isopropyl tricumylphenyl titanate; aluminum coupling agents such as acetoalkoxyaluminum diisopropylate; zirconium coupling agents such as acetylacetone / zirconium complex. Can be mentioned.

Examples of the ultraviolet absorber include benzophenone or a benzophenone derivative, phenyl salicylate or a phenyl salicylate derivative, benzotriazole or a benzotriazole derivative. Particularly, benzotriazole type is preferable. As the antioxidant, a hindered amine type is particularly preferable.

Further, as a solvent used as necessary, aromatic hydrocarbons such as toluene and xylene, ethyl acetate of alcohols such as methanol, ethanol and isopropyl alcohol, esters such as ethicero, methicello and cellosolve acetate, methyl ethyl ketone, Examples thereof include ketones such as methyl isobutyl ketone and cyclohexanone. These solvents may be used alone or in combination of two or more. To obtain the active energy ray-curable resin composition for silver coating of the present invention, the above-mentioned components may be mixed, and the order and method of mixing are not particularly limited.

The active energy rays used herein refer to ultraviolet rays, electron rays, ionizing radiation such as α rays, β rays, γ rays, microwaves, high frequencies, etc., provided that radical active species can be generated. , Any kind of energy will do. It may be visible light, infrared light, or laser light.

Examples of the ultraviolet ray generators include ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, metal halide lamps, chemical lamps, black light lamps, mercury-xenon lamps, short arc lamps, helium / cadmium lasers, and argon lasers. And may be selected in consideration of the absorption wavelength of the compound that generates the radical active species.

Applications of silver for which the coating agent of the present invention excellent in imparting discoloration (corrosion) resistance is used include lighting equipment, ornaments, electronic materials, semiconductor materials, aerospace materials, and various other industrial materials. In particular, a slight discoloration (corrosion) occurs in a lighting fixture in which a thin silver film is formed on the light reflecting surface by vapor deposition.
However, the coating agent of the present invention can be effectively used because it has a great influence.

The coating method of the present invention which is excellent in imparting discoloration resistance (corrosion) resistance to the silver surface includes, for example, flow coater coating, spray coating and depping coating, which are suitable for the shape of the article to be coated. You just have to choose. Appropriate film thickness is 3-30μ, but among them, discoloration resistance (corrosion)
From the standpoint of durability and durability, 8 to 15 μm is preferable.

[0130]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. In the examples, all parts are parts by weight unless otherwise specified.

Reference Example 1 Synthesis Example of Saturated Compound (A) Having Hydrolyzable Silyl Group 42.5 parts of methyl methacrylate, 18.0 parts of 2-hydroxyethyl methacrylate, n-butyl methacrylate 2
7.5 parts, 5.0 parts of n-butyl acrylate, 5.0 parts of 3-methacryloxypropyltrimethoxysilane, methacryloxypropyldimethylpolysiloxane with one terminal (Mw
= 5,000) 1.0 part, methacrylic acid 1.0 part and azobisisobutyronitrile 2.0 parts were mixed to prepare a monomer mixture for polymerization.

This mixture was purged with nitrogen and added dropwise to 233 parts of a mixture of isopropyl alcohol and ethyl acetate (3/1 by weight) kept at 80 ° C. with stirring.
The temperature was kept at 80 ° C. for 3 hours to obtain an acrylic copolymer. A mixed solution of isopropyl alcohol and ethyl acetate (3/1 by weight ratio) was added to this acrylic copolymer to adjust the solid content to 20% to obtain an acrylic copolymer (1). The acrylic copolymer (1) has a weight average molecular weight of 5,80.
0, the amount of hydrolyzable silyl group is 201 mmol / Kg
(Resin content).

Reference Example 2 Synthesis Example of Saturated Compound (A) Having Hydrolyzable Silyl Group A 4-necked flask was charged with 742.11 parts of 3-isocyanatopropyltriethoxysilane and 0.20 g of dibutyltin dilaurate. , While stirring, the reaction temperature is 60 ~
While maintaining at 65 ° C., tris (2-hydroxyethyl) isocyanurate (Tanac manufactured by Nissan Chemical Co., Ltd.) 261.24
g was added dropwise.

After dropping, the mixture was reacted at 65 ° C. for 4 hours, and then IR
Then, it was confirmed that the peak based on the isocyanate group had disappeared, the reaction was terminated, and a compound (2) having a hydrolyzable silyl group was obtained. The amount of hydrolyzable silyl groups in the compound (2) was 2989 mmol / Kg (resin content).

Reference Example 3 Synthesis example of unsaturated compound (B) having radically polymerizable unsaturated double bond: 42.5 parts of methyl methacrylate, 18.0 parts of 2-hydroxyethyl methacrylate, n-methacrylic acid Butyl 2
7.5 parts, n-butyl acrylate 10.0 parts, one-terminal methacryloxypropyl dimethyl polysiloxane (Mw =
5,000) 1.0 part, methacrylic acid 1.0 part and azobisisobutyronitrile 1.0 part were mixed to prepare a monomer mixture for polymerization.

This mixed solution was purged with nitrogen and added dropwise to 100 parts of methyl ethyl ketone kept at 80 ° C. with stirring. After dropping, the mixture was kept at 80 ° C. for 8 hours to obtain an acrylic copolymer. To this acrylic copolymer, 1.33 g of BHT, 0.199 g of metoquinone, and 0.10 g of dibutyltin dilaurate.
133 g was added, and the reaction temperature was adjusted to 60 to 65 while stirring.
While maintaining at 0 ° C, 21.4 parts of 2-isocyanatoethyl methacrylate was added dropwise, followed by reaction at 65 ° C for 4 hours, and the reaction was terminated by confirming that the peak based on the isocyanate group disappeared by IR. Then, methyl ethyl ketone was added to the mixture to adjust the solid concentration to 20% to obtain an acrylic copolymer (3) having a methacrylic group. The weight average molecular weight of the acrylic copolymer (3) was 48,000.

Reference Example 4 Synthesis Example of Unsaturated Compound (C) Having Hydrolyzable Silyl Group and Radical Polymerizable Unsaturated Bond Methyl methacrylate 42.5 parts, 2-hydroxyethyl methacrylate 18.0 parts, N-butyl methacrylate 2
7.5 parts, n-butyl acrylate 10.0 parts, one-terminal methacryloxypropyl dimethyl polysiloxane (Mw =
5,000) 1.0 part, methacrylic acid 1.0 part and azobisisobutyronitrile 1.0 part were mixed to prepare a monomer mixture for polymerization.

This mixture was purged with nitrogen and added dropwise to 100 parts of methyl ethyl ketone kept at 80 ° C. with stirring. After the dropping, the mixture was kept at 80 ° C. for 8 hours to obtain an acrylic copolymer. 1.33 g of BHT was added to this acrylic copolymer,
0.199 g of methoquinone and 0.133 g of dibutyltin dilaurate were added, and the reaction temperature was 60 to 60% with stirring.
While maintaining the temperature at 65 ° C, 10.7 parts of 2-isocyanatoethyl methacrylate was dropped, and after the dropping, at 65 ° C for 4 hours,
After the reaction, it was confirmed by IR that the peak based on the isocyanate group had disappeared, and the reaction was terminated.

Further, dibutyltin dilaurate 0.13
3 g was added, 17.1 parts of 3-isocyanatopropyltriethoxysilane was added dropwise while stirring and maintaining the reaction temperature at 60 to 65 ° C., and after the addition, the reaction was carried out at 65 ° C. for 4 hours, and the isocyanate group was changed by IR. After confirming the disappearance of the peak based on the above, the reaction was terminated, and methyl ethyl ketone was added to adjust the solid content concentration to 20% to obtain an acrylic copolymer (4) having a methacryl group and a triethoxysilyl group. . The acrylic copolymer (4) has a weight average molecular weight of 58,000 and a hydrolyzable silyl group content of 541 mm.
It was ol / Kg (resin content).

Reference Example 5 Synthesis Example of Unsaturated Compound (C) Having Hydrolyzable Silyl Group and Radical Polymerizable Unsaturated Bond A 4-necked flask was charged with 247.4 parts of 3-isocyanatopropyltriethoxysilane. BHT 1.33g, methquinone 0.199g, dibutyltin dilaurate 0.13
While adding 3 g and maintaining the reaction temperature at 60 to 65 ° C. with stirring, diacrylate of tris (hydroxyethyl) isocyanurate (Aronix M21 manufactured by Toagosei Co., Ltd.
5) 416.5 g was added dropwise.

After the dropping, the mixture was reacted at 65 ° C. for 4 hours, and IR
Then, it was confirmed that the peak based on the isocyanate group had disappeared, the reaction was completed, and the hydrolyzable silyl group-containing 2
A functional acrylate compound (5) was obtained. The amount of hydrolyzable silyl groups in the compound (5) was 1506 mmol / Kg (resin content).

Reference Example 6 Synthesis Example of Acrylic Polymer (D) Not Having Hydrolyzable Silyl Group and Radical Polymerizable Unsaturated Double Bond 42.5 parts of methyl methacrylate, 2-hydroxyethyl methacrylate 18 0.0 parts, n-butyl methacrylate 2
7.5 parts, tetrahydrofurfuryl acrylate 5.0
Parts, tetrahydrofurfuryl methacrylate 5.0 parts,
Monomer for polymerization by mixing 1.0 part of methacryloxypropyldimethylpolysiloxane with one terminal (Mw = 5,000), 1.0 part of methacrylic acid and 1.0 part of t-butylperoxy 2-ethylhexanoate. A body mixture was prepared.

This mixture was purged with nitrogen and added dropwise to 100 parts of methyl ethyl ketone kept at 80 ° C. with stirring. After the dropping, the mixture was kept at 80 ° C. for 3 hours to obtain an acrylic copolymer. Methyl ethyl ketone was added to this acrylic copolymer to adjust the solid content concentration to 20% to obtain an acrylic copolymer (1). The weight average molecular weight of the acrylic copolymer (6) was 720,000.

(Examples 1 to 6) and (Comparative Examples 1 to 6) Raw materials were blended in the compositions shown in Tables 1 and 2 to prepare resin compositions for use in the present invention and for comparison. Then, it is applied on the surface of vapor-deposited silver by a spray method so that the film thickness after curing becomes 10 μm, dried at 70 ° C. for 20 minutes, and then 120 W / cm in the atmosphere.
Using a high-pressure mercury lamp (manufactured by Eye Graphics Co., Ltd.), the lamp height is 15 cm and the conveyor speed is 30 m
Ultraviolet rays were irradiated under the condition of minutes to obtain a vapor-deposited silver film having a cured coating film.

The performance was evaluated by the following tests. The results are shown in Tables 3 and 4. Saturated compounds having a hydrolyzable silyl group in Tables 1 and 2; (A-1), (A-2), unsaturated compounds having a radical-polymerizable unsaturated double bond;
(B-1), (B-2), an unsaturated compound having a hydrolyzable silyl group and a radical-polymerizable unsaturated bond; (C-
1), (C-2), a saturated compound having no hydrolyzable silyl group and radically polymerizable unsaturated double bond; (D-
1), curing catalyst; (E-1), photopolymerization initiator; (F-
1) and additives; (G-1) and (G-2) are as follows.

A-1: Resin Component of Acrylic Copolymer (1) A-2: Compound (2) B-1: Resin Component of Acrylic Copolymer (3) B-2: Aronix M215 (Toagosei Co., Ltd.) ) = Diacrylate of tris (hydroxyethyl) isocyanurate

C-1: Resin Component of Acrylic Copolymer (4) C-2: Compound (5) D-1: Resin Component of Acrylic Copolymer (6) E-1: Dibutyltin Dilaurate F-1: Darocure 1173 (manufactured by Ciba Geigy) G-1: Hindered amine antioxidant Sanol LS-
292 (manufactured by Sankyo Co.) G-2: Benzotriazole-based UV absorber Tinuvin 9
00 (Ciba Geigy)

Further, in the Examples and Comparative Examples, the adhesion, moisture resistance test and hydrogen sulfide gas resistance test were evaluated and measured by the following methods. (1) Adhesion: Make nicks that reach the evaporated silver surface of the base from the painted surface so that 100 squares of 1.00 mm square can be made, and stick cellophane tape well on it and peel off vigorously Expressed as a leading number.

(2) Moisture resistance test: 40 ° C., relative humidity 95
% Of the sample in a constant temperature and humidity chamber (manufactured by Takeda Riken Co., Ltd.) and then at room temperature for 24 hours, and the degree of discoloration (corrosion) on the surface of the vapor-deposited silver was evaluated according to the following four grades. A: No discoloration (corrosion) is observed. ○: Almost no discoloration (corrosion) is observed. Δ: Discoloration (corrosion) is recognized. X: Significant discoloration (corrosion) is recognized.

(3) Hydrogen sulfide gas resistance test: After the sample was left for 150 hours in a desiccator adjusted to a hydrogen sulfide gas concentration of 20 ppm in an atmosphere of 25 ° C., the adhesion and the surface of the vapor-deposited silver were tested in the same manner as above. The degree of change (corrosion) was evaluated.

[0151]

[Table 1]

[0152]

[Table 2]

[0153]

[Table 3]

[0154]

[Table 4]

[0155]

INDUSTRIAL APPLICABILITY The present invention has excellent adhesion to the surface of silver, can sufficiently exhibit the spreadability and beautiful surface appearance that silver originally has, and can prevent discoloration (corrosion) of silver. It is possible to provide an active energy ray-curable resin composition for silver coating having excellent durability.

Claims (11)

[Claims] 1. A hydrolyzate containing 10 to 95% by weight of a saturated compound (A) having a hydrolyzable silyl group and 5 to 90% by weight of an unsaturated compound (B) having a radical-polymerizable unsaturated double bond. Degradable silyl group 0.5-2,000 mmol
/ Kg contained active energy ray curable resin composition for silver coating. 2. 0.5 to 2,000 mmol of a hydrolyzable silyl group containing an unsaturated compound (C) having a hydrolyzable silyl group and a radically polymerizable unsaturated bond in one molecule.
/ Kg contained active energy ray curable resin composition for silver coating. 3. The active energy ray-curable resin composition for silver coating according to claim 1, wherein the saturated compound (A) having a hydrolyzable silyl group is a radical polymer. 4. The active energy ray-curable resin composition for silver coating according to claim 1, wherein the unsaturated compound (B) having a radically polymerizable unsaturated double bond is a radical polymer. 5. The silver coating activity according to claim 2, wherein the unsaturated compound (C) having a hydrolyzable silyl group and a radical polymerizable unsaturated bond in one molecule is a radical polymer. Energy ray curable resin composition. 6. The weight average molecular weight of the radical polymer is
The active energy ray-curable resin composition for silver coating according to claim 3, which is 5,000 to 800,000. 7. The weight average molecular weight of the radical polymer is
The active energy ray-curable resin composition for silver coating according to claim 4, which is 5,000 to 800,000. 8. The weight average molecular weight of the radical polymer is
The active energy ray-curable resin composition for silver coating according to claim 5, which is 5,000 to 800,000. 9. A saturated compound (A) containing a hydrolyzable silyl group and / or an unsaturated compound (C) 9 having a hydrolyzable silyl group and a radical polymerizable unsaturated bond in one molecule.
0-99.99% by weight and curing catalyst (E) 0.01-1
The active energy ray-curable resin composition for silver coating according to any one of claims 1 to 8, characterized in that it contains 0% by weight. 10. An unsaturated compound (B) having a radical-polymerizable unsaturated double bond and / or an unsaturated compound (C) having a hydrolyzable silyl group and a radical-polymerizable unsaturated bond in one molecule (C) 80- 99.9% by weight and 0.1 to 20% by weight of a photopolymerization initiator (F), The active energy ray curable type for silver coating according to any one of claims 1 to 8, characterized in that Resin composition. 11. A silver coating, characterized in that 5 to 95% by weight of the resin composition according to any one of claims 1 to 10 further contains 5 to 95% by weight of an acrylic copolymer (D). Energy ray curable resin composition for use.