JPH09241532A - Coating composition for silver - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating compsn. for silver which imparts a protective coating film excellent in preventing discoloration of silver by combining a specific main film-forming component with a specific metal deactivator. SOLUTION: This compsn. contains a resin component, as the main film- forming component, which has hydrolyzable silyl groups and reactive basic nitrogen groups and/or groups having free-radical-polymerizable double bonds and is curable by water in the air at normal temp. or by an active energy ray and 0.01-5wt.% (based on the resin in the compsn.) dicarboxylic acid-added deriv. of mercaptobenzothiazole as a silver-deactivating component. A pref. normal-temp.-curable resin component has hydrolyzable groups bonded to an acrylic main chain and is curable by water in the air to form a siloxane-acrylic copolymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is excellent in preventing discoloration (corrosion) of silver in various silver products such as ornaments, tableware, electronic parts, and lighting equipment, and particularly excellent in discoloration resistance on a silver vapor deposition surface. The present invention relates to a coating agent having a room temperature curability or an actinic energy ray curability, that is, a composition for a silver-coated paint that can be given.

[0002]

2. Description of the Related Art Silver has been used as a noble metal as a decoration, currency, tableware, electronic material, and dental material for a long time by utilizing its excellent optical properties and electrochemical properties. Its applications have rapidly increased as photographic industrial materials, semiconductor materials, conductive materials, aviation and space materials, and are widely used as industrial materials.

[0003] However, silver materials used in these applications are extremely unstable chemically, and easily react with oxygen, moisture, hydrogen sulfide, sulfur dioxide and the like in the air to produce silver oxide and silver sulfide. This has the disadvantage that the silver surface is discolored (corroded) to brown or black.

As a method for preventing such discoloration (corrosion), silver is replaced with another metal such as copper, platinum, palladium, or the like.
Although a method of forming an alloy with iridium, zinc, tin or the like, or applying an epoxy resin or the like to the surface is known, the former method has drawbacks such as poor spreadability and poor surface appearance. In the latter case, it is difficult to prevent discoloration (corrosion) on the silver surface for a long period of time due to insufficient adhesion to the silver surface or insufficient durability.

[0005]

Therefore, in order to fully exhibit the excellent spreadability and the beautiful appearance of the surface originally possessed by silver, it is necessary to perform the coating protection treatment on the surface of silver itself, not by the alloy treatment. It has been found that a new solution is needed, and for that purpose, the search for a new type of coating agent having improved adhesion to a silver surface and durability is a problem to be solved at present. . As a result, a new invention relating to the composition of the resin component, which is the base component of the coating agent, has been made,
Japanese Patent Application No. 5-138406 (JP-A-6-57198)
No.) and No. 7-51113.

Although these inventions have found a temporary solution to the above-mentioned problems, there is an infinite demand for further improvement in performance, and further effective measures for enhancing the protective performance of the silver surface are sought. Was given.

[0007]

DISCLOSURE OF THE INVENTION In view of the above situation, the present inventor has conducted diligent research, and as a result, from among various substances known as metal deactivators, the above-mentioned novel coating substrate component was selected. We searched for substances that work together to achieve more effective protection of the silver surface. As a result, it was determined that a specific metal deactivator is effective as a silver deactivator in combination with the above-mentioned specific coating film substrate component, whereby a coating composition excellent in silver discoloration (corrosion) prevention property is obtained. The inventors have found that the following can be obtained, and have completed the present invention.

That is, the present invention provides, as a coating substrate component,
Having a hydrolyzable silyl group and a reactive group having a basic nitrogen atom and / or a group having a radical-polymerizable unsaturated double bond, and having room temperature curability by moisture in the air or curing by active energy rays A silver coating composition containing a resin component having properties, wherein the coating resin contains 0.01 to 5% by weight of a carboxylic acid addition derivative (I) of mercaptobenzothiazole as a silver inactivating component. The present invention relates to a silver coating composition.

In such a composition, a room temperature-curable resin component having a hydrolyzable silyl group in the acrylic main chain and forming a siloxane-acrylic copolymer by the moisture in the air and curing Is preferred as the first
Are listed in.

Further, such a room temperature curable resin component is
(A) an acrylic vinyl polymer containing a reactive group having a basic nitrogen atom, (B) a compound containing a hydrolyzable silyl group and an epoxy group in one molecule, and a component A A two-component system in which the mixing ratio with the B component is within the range of 0.2 to 5 equivalents of the epoxy group contained in the B component with respect to 1 equivalent of the reactive group contained in the A component. It is suitable.

The acrylic vinyl polymer (A)
Is obtained by reacting a vinyl-based monomer having at least one group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, various carboxylic acid amide groups, and a cyano group. Polymers are preferred.

As the compound (B), γ-glycidoxypropylalkoxysilane and / or γ-glycidoxypropyltriisopropenyloxysilane or an adduct of γ-isocyanatopropyltriisopropenyloxysilane and glycidol. Alternatively, an adduct of γ-aminopropyltrimethoxysilane and the like and a diethoxy compound is preferable.

The compound (B) is preferably a vinyl polymer containing an epoxy group and a hydrolyzable silyl group at the main chain terminal and / or side chain.

As the active energy ray-curable resin component in the composition of the present invention, a saturated compound (C) having a hydrolyzable silyl group and an unsaturated compound (D) having a radical-polymerizable unsaturated double bond are used. A two-component system containing is first mentioned as a suitable one.

However, as the active energy ray-curable resin component, those containing an unsaturated compound (E) having a hydrolyzable silyl group and a radical-polymerizable unsaturated double bond in one molecule are also suitable.

Throughout the present invention, the hydrolyzable silyl group is preferably a group represented by the following general formula (1). General formula (1)

[0017]

Embedded image [Wherein R ₁ represents a hydrogen atom or one organic group consisting of an alkyl group or an aralkyl group, and R ₂ represents a halogen atom or a hydroxyl group, an alkoxy group, an acyloxy group, a phenoxy group, an iminooxy group or an alkenyloxy group. And a is a natural number of 0, 1 or 2. ]

In the present invention, the silver to be coated may be not only solid silver but also thin layer silver,
In particular, when the surface is a silver vapor-deposited surface, the effect of the invention is remarkably exhibited.

Throughout the present invention, a typical example of the dicarboxylic acid addition derivative (I) of mercaptobenzothiazole is (2-benzothiazolylthio).
-Succinic acid.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a resin having a hydrolyzable silyl group that imparts room temperature curability by moisture in the air and serving as a coating film substrate component is preferably an acrylic main group containing a hydrolyzable silyl group. A substance introduced into a chain, which forms a siloxane-acrylic copolymer by moisture in the air and cures (hereinafter simply referred to as a silicon acrylic resin).

The room temperature curable silicone acrylic resin used in the present invention has a hydrolyzable silyl group represented by the above-mentioned general formula (1). Typical examples of such a group are as follows. , Hydroxyl group or halogen group, epoxy group,
Hydroxysilyl group, halosilyl group, alkoxysilyl group, phenoxysilyl group, iminooxysilyl group, alkenyloxysilyl group containing functional groups such as alkoxy group, acyloxy group, amide group, phenoxy group, iminooxy group and alkenyloxy group. There are organosilicon-containing reactive groups that are susceptible to hydrolysis, such as

Such a coating composition may further contain a catalyst for hydrolysis-condensation, a solvent, a leveling agent, a defoaming agent, if necessary.
Known additives such as matting agents, ultraviolet absorbers and antioxidants can also be added.

As the hydrolysis-condensation catalyst used as required, basic compounds such as lithium hydroxide and potassium hydroxide, metal-containing compounds such as tetraisopropyl titanate and tin octylate, and p-toluenesulfonic acid. ,
There are acidic compounds such as dialkyl phosphoric acid.

As a solvent used as required, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol and isopropyl alcohol,
Esters such as ethyl acetate, ethicello, methicello, and cellosolve acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; These solvents may be used alone or in a combination of two or more.

The room temperature curable silicone acrylic resin of the present invention includes (A) an acrylic vinyl polymer containing a reactive group having a basic nitrogen atom, (B) an epoxy group in one molecule, and A compound containing a hydrolyzable silyl group represented by the formula (1) is contained, and the mixing ratio of the A component and the B component is such that the reactive group such as an amino group contained in the A component. A resin composition having an epoxy group content of 0.2 to 5 equivalents relative to 1 equivalent, which reacts with each other when a coating film is formed, Precursors such as those that form silicone acrylics are also included as substantially equivalent.

If necessary, this precursor composition also contains
Further, known additives similar to the above, such as a hydrolysis-condensation catalyst, a solvent, a leveling agent, a defoaming agent, a matting agent, an ultraviolet absorber and an antioxidant can be added.

As the acrylic vinyl polymer (A) containing a reactive group having a basic nitrogen atom used in the present invention, at least one basic nitrogen atom in one molecule, that is, a primary amino group or a secondary amino group, is used. Group, and a tertiary amino group, various carboxylic acid amide group, sulfonamide group, an acrylic vinyl monomer containing a reactive group having at least one basic nitrogen atom selected from the group consisting of cyano group, It can be prepared by (co) polymerization by a known method.

Specific examples of such an acrylic vinyl monomer containing a basic nitrogen atom include dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth).
Various dialkylaminoalkyl (meth) acrylates such as acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylamide, N-diethylaminoethyl (meth) acrylamide, N-dimethyl N-dialkylaminoalkyl (meth) acrylamides such as aminopropyl (meth) acrylamide, trialkylaminoalkyl (meth) acrylates such as t-butylaminoethyl (meth) acrylate, t-butylaminopropyl (meth) acrylate, Various carboxylic acid amide group-containing vinyl monomers such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-alkoxymethyl (meth) acrylamide, pose Ren sulfonamide, N- methyl-p-styrene sulfonamide various sulfonamide group-containing vinyl monomers such as include (meth) cyano group-containing vinyl monomers and the like, such as acrylonitrile.

These acrylic vinyl polymers (A) containing a basic nitrogen atom may be used alone or in combination of two or more. Of these, preferred are various dialkylaminoalkyl (meth) acrylates and N-dialkylaminoalkyl (meth) acrylates.
Acrylamides, carboxylic acid amide group-containing vinyl monomers, and cyano group-containing vinyl monomers, particularly preferred are dialkylaminoalkyl (meth) acrylates and N-dialkylaminoalkyl (meth) acrylamides. is there.

The acrylic vinyl polymer (A) containing such a basic nitrogen atom can be used by copolymerizing it with another vinyl monomer, if necessary. Specific examples of the copolymerizable vinyl-based monomer include various (meth) acrylic acid esters such as methyl (meth) acrylate, n-propyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, and (meth). Carboxyl group-containing vinyl monomers such as acrylic acid, maleic acid and itaconic acid, maleic anhydride, acid anhydride group-containing vinyl monomers such as itaconic anhydride, p-styrene sulfonic acid, 2-acrylamido-2- Examples thereof include sulfonic acid group-containing vinyl monomers such as methylpropane sulfonic acid, various vinyl esters such as vinyl acetate and vinyl benzoate, and fluorine-containing vinyl monomers.

These copolymerizable vinyl-based monomers are 1
The seeds may be used alone or in combination of two or more.

The compound (B) containing an epoxy group and a hydrolyzable silyl group represented by the general formula (I) in one molecule means a vinyl polymer or an epoxy group containing both types of reactive groups. And a silane coupling agent containing

Any known method can be applied to prepare the above-mentioned vinyl polymer containing both types of reactive groups, but γ- (meth) acryloyloxypropyltrimethoxysilane and γ- (meth ) Vinyl-based monomers having a hydrolyzable silyl group such as acryloyloxypropyltriisopropenyloxysilane, and vinyl having an epoxy group such as (β-methyl) glycidyl (meth) acrylate and di (β-methyl) glycidylmalate Examples include a method of solution radical polymerization with a system monomer.

Next, specific examples of the above-mentioned epoxy group-containing silane coupling agent include γ-glycidoxy proxy trimethoxy silane, γ-glycidoxy propyl triethoxy silane and γ-glycidoxy propyl methyl diethoxy silane. , Γ-glycidoxypropyltriisopropenyloxysilane, an adduct of γ-isocyanatopropyltriisopropenyloxysilane or the like with glycidol, or an adduct of γ-aminopropyltrimethoxysilane or the like with a diepoxy compound. Among them, preferred are γ-glycidoxytrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ
-Glycidoxypropyltriisopropenyloxysilane, and particularly preferred is γ-glycidoxy proxy trimethoxysilane.

The mixing ratio of the component A and the component B in the coating composition of the present invention is such that the epoxy group present in the component B is equivalent to 1 equivalent of the reactive group such as amino group present in the component A. It is in the range of 0.2 to 5 equivalents. Above all 0.2
A range of 2 equivalents is particularly preferred.

If the proportion of the component B used is less than 0.2 equivalent, sufficient reactivity cannot be obtained, and the discoloration (corrosion) resistance of silver cannot be obtained. If it exceeds 5 equivalents, the storage stability of the paint, Adhesion is lowered, which is not preferable.

Another type of resin used as a coating substrate component in the present invention, a resin curable by active energy rays, is a group having a hydrolyzable silyl group and a radically polymerizable unsaturated double bond. It is a resin having.

As such a resin component, a two-component system containing a saturated compound (C) having a hydrolyzable silyl group and an unsaturated compound (D) having a radical-polymerizable unsaturated double bond is preferable. As described above, the saturated compound (C) having a hydrolyzable silyl group is 10 to 95% by weight, and the unsaturated compound (D) having a radical-polymerizable unsaturated double bond is 5 to 90% by weight. %, Each containing 0.5 to 2,000 mmol / Kg of hydrolyzable silyl group is more preferable.

The active energy ray-curable resin component is an unsaturated compound (E) having a hydrolyzable silyl group and a radical-polymerizable unsaturated bond in one molecule, and the hydrolyzable silyl group is 0.1. Those containing 5 to 2,000 mmol / Kg are also suitable.

More specifically, in particular, a saturated compound (C) having a hydrolyzable silyl group, an unsaturated compound (D) having a radical-polymerizable unsaturated double bond, and a hydrolyzable silyl group and a radical in one molecule. The unsaturated compound (E) having a polymerizable unsaturated bond is a radical polymer.

These (C) and (D) used as the active energy ray-curable resin component for silver coating of the present invention.
The radical polymer (E) having a weight average molecular weight of 5,000 to 800,000 is particularly preferable because it has good adhesion to silver.

The present invention also relates to a saturated compound (C) containing a hydrolyzable silyl group and an unsaturated compound (E) 90 to 99.n having a hydrolyzable silyl group and a radical-polymerizable unsaturated bond in one molecule. 99% by weight and curing catalyst (G) 0.
The coating film base component may be one containing from 0.1 to 10% by weight, and the unsaturated compound (D) having a radical polymerizable unsaturated double bond and a hydrolyzable silyl group in one molecule. And 80% to 99.9% by weight of an unsaturated compound (E) having a radical-polymerizable unsaturated bond and 0.1 to 20% by weight of a photopolymerization initiator (H) as a coating substrate component. May be

Furthermore, in the present invention, the above-mentioned resin compositions 5 to 9 are used.
In addition to 5% by weight, the coating substrate component containing 5 to 95% by weight of the acrylic copolymer (F) is also included.

The hydrolyzable silyl group referred to in the present invention may be any hydrolyzable silyl group, for example, the one represented by the general formula (1) as described above.

As described above, the hydrolyzable silyl group contains a functional group such as a hydroxyl group, a halogen group, an epoxy group, an alkoxy group, an acyloxy group, an amide group, a phenoxy group, an iminooxy group and an alkenyloxy group. There are organic silicon-containing reactive groups such as a hydroxysilyl group, a halosilyl group, an alkoxysilyl group, a phenoxysilyl group, an iminooxysilyl group and an alkenyloxysilyl group, which are easily hydrolyzed.

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 allyl group, a maleimide group and a (meth) acrylamide group.

The active energy ray-curable resin component of the present invention is characterized in that the resin contains a hydrolyzable silyl group and a radically polymerizable unsaturated double bond. The saturated double bond 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 component containing a hydrolyzable silyl group and a radical-polymerizable unsaturated double bond of the present invention comprises a saturated compound (C) having a hydrolyzable silyl group and a radical-polymerizable unsaturated bond. An unsaturated compound (D) having a double bond and / or an unsaturated compound (E) having a hydrolyzable silyl group and a radical-polymerizable unsaturated bond in one molecule are essential components, and a hydrolyzable silyl group and An acrylic copolymer (F) having no radically polymerizable unsaturated double bond, a curing catalyst (G), and a photopolymerization initiator (H) are optionally contained.

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

The unsaturated compound (E) having a hydrolyzable silyl group and a radical-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 (C) (D).

Examples of the saturated compound (C) having a hydrolyzable silyl group include a silane coupling agent (C1), an oligomerization product of an alkoxysilyl compound (C2), and a compound (C in which a hydrolyzable silyl group is grafted to a saturated compound.
3) and so on. As the silane coupling agent (C1),
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 (C11) 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 (C
Typical examples of 12) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane. , Γ-glycidoxypropyltriisopropenyloxysilane, γ-glycidoxypropyltriiminooxysilane,

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

Amino group-containing silane coupling agent (C1
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 (C1
Typical examples of 4) include γ-chloropropyltrimethoxysilane and γ-chloropropylmethyldimethoxysilane. Typical examples of the isocyanate group-containing silane coupling agent (C15) include 3-isocyanatopropyltriethoxysilane.

The oligomerization product (C2) of an alkoxysilyl compound means, as an alkoxysilyl compound, tetraalkoxysilane such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane, 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 (C3) grafted with a hydrolyzable silyl group is a compound (C31) 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 (C32) obtained by reacting a silicon hydride compound with 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. (C33) etc.

In the compound (C31) 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 a combination of mercapto group / radical polymerizable group (the same applies below), 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 There are groups, etc.

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 (C16), or a radical-polymerizable double bond group-containing resin, a mercapto group-containing silane coupling agent (C11) Resin reacted with hydroxyl group-containing resin, isocyanate group-containing silane coupling agent (C15) reacted, isocyanate group-containing resin reacted with amino group-containing silane coupling agent (C13), carboxyl Examples of the group-containing resin include a resin obtained by adding an epoxy group-containing silane coupling agent (C12).

Typical examples of the radical polymerizable double bond group-containing silane coupling agent (C16) include γ- (meth) acryloyloxypropyltrimethoxysilane.
γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, γ- (meth) acryloyloxypropyltripropenyloxysilane, γ- (meth) acryloyloxypropyltriiminooxysilane , Vinyltrimethoxysilane, vinyltriethoxysilane, vinyl (tris-β-methoxyethoxy) silane, vinyltriacetoxysilane, vinyltrichlorosilane, N-β- (N-vinylbenzylaminoethyl)-
γ-aminopropyltrimethoxysilane, hydrochloride, etc.

In the compound (C32) obtained by reacting the compound (C32-2) having an olefin group with the silicon hydride compound (C32-1), the silicon hydride compound (C32-1) 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 (C32-2) having an olefin group, examples of the olefin group include those represented by the general formula (2).

General formula (2)

[0071]

CH2 = CH (R1) -R2-- (wherein R1 is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and R2 is the same or different divalent group having 1 to 20 carbon atoms). Indicates an organic group)

As the compound (C32-2) 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 (C32-1) and the compound having an olefin group (C32-2) 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 (C33) obtained by radically copolymerizing a heavy bond-containing unsaturated compound includes radically polymerizable 2
A heavy bond group-containing silane coupling agent (C16) and / or a mercapto group-containing silane coupling agent (C11),
There is a radical polymer obtained by radically copolymerizing a radically polymerizable double bond-containing unsaturated compound (C33-1).

As the radically polymerizable double bond-containing unsaturated compound (C33-1), 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 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.

Upon 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.

The 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.

The unsaturated compound (D) having a radical-polymerizable unsaturated double bond includes a prepolymer (D1) having a radical-polymerizable property and a monomer (D2) having a radical-polymerizable property. Examples of the radical-polymerizable prepolymer (D1) include urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, polybutadiene (meth) acrylate having a molecular weight of 500 or more.

(Meth) acrylic compounds such as silicone (meth) acrylates, polyether (meth) acrylates, melamine (meth) acrylates, phosphazene (meth) acrylates and acrylic copolymers having (meth) acryloyl groups 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 (D2) 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 (meth) acrylic compounds, 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 (D2) 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 (D) 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) acrylates of hydrogenated bisphenols, di (meth) acrylates of modified alkylene oxides of hydrogenated bisphenols, and di (meth) acrylates of modified alkylene oxides of trisphenols. 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 modified alkylene oxide 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 (E) having a hydrolyzable silyl group and a radical-polymerizable unsaturated bond include:
Radical-polymerizable double bond group-containing silane coupling agent (C16) and unsaturated compounds having functional groups that react with the functional groups of the silane coupling agent and the silane coupling agent (E
There is a compound (E1) obtained by reacting 11).

In the compound (E1) 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 (E1), 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 ones are not limited to the functional groups of the silane coupling agent, but may be the functional groups of the unsaturated compound. For example, (1); a compound obtained by reacting a hydroxyl group-containing radically polymerizable unsaturated compound (E11-1) with an isocyanate group-containing silane coupling agent (C15).

As the hydroxyl group-containing radically polymerizable unsaturated compound (E11-1), 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.

As the allyl compound having a hydroxyl group, pentaerythritol triallyl ether, trimethylolpropane diallyl ether, 2-propen-1-ol, 4-hydroxybutyl allyl ether, etc., and as the vinyl ether compound having a hydroxyl group, ethylene glycol mono 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 (C11) or an amino group-containing silane coupling agent (C13) 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. Compounds with groups (E
Compounds obtained by reacting 11-2).

As the compound (E11-2) having 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, (meth) acrylic acid, etc. In addition to the carboxyl group-containing radically polymerizable unsaturated compound of (3), an epoxy group-containing silane coupling agent such as γ-glycidoxypropyltrimethoxysilane (C
12) reacted,

An epoxy group-containing unsaturated compound such as glycidyl (meth) acrylate is reacted with an amino group-containing silane coupling agent (C13) such as γ-aminopropyltrimethoxysilane or a mercapto group-containing silane coupling agent (C11). Examples thereof include those obtained by reacting two or more hydroxyl group-containing radically polymerizable unsaturated compounds with an isocyanate group-containing silane coupling agent (C15) such as isocyanatopropyltrimethoxysilane.

(4): Polyisocyanate compound (E11
-3), an amino group-containing silane coupling agent (C13),
A silane coupling agent containing an active hydrogen group such as a mercapto group-containing silane coupling agent (C11) or an epoxy group-containing silane coupling agent (C12) is used as an isocyanate group of 50
Up to 90% addition reaction, and the remaining isocyanate group is reacted with a hydroxyl group-containing radically polymerizable unsaturated compound (E11-1).

Examples of the polyisocyanate compound (E11-3) 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 (F), 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 include halogens, epoxy groups, amino groups, hydroxyl groups, thiol groups,
You may have functional groups, such as an amide group, a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

As the curing catalyst (G) used as required, 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 addition amount of the curing catalyst (G) is a saturated compound (C) having a hydrolyzable silyl group and an unsaturated compound (C) having a hydrolyzable silyl group and a radical polymerizable unsaturated bond in one molecule ( Resin composition 90 to 9 comprising E)
Usually, 0.01 to 10% by weight is added to 9.99% by weight. 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 (H) a photopolymerization initiator to the resin composition. The amount of the photopolymerization initiator added is a resin composition comprising an unsaturated compound (D) having a radical polymerizable unsaturated double bond and an unsaturated compound (E) having a hydrolyzable silyl group and a radical polymerizable unsaturated bond. 80 to 99.9% by weight, usually 0.1 to 20
% By weight, preferably 0.5 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 photopolymerization initiator can be roughly classified into two types, that is, one that produces an active species when a bond is cleaved in the molecule by light and one that 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-
Acetophenones such as (4-morpholinophenyl) -butanone; benzoins such as benzoin, benzoin isopropyl ether and 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,
Benzophenones 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 can be 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 compounding amount of the photosensitizer is a resin composition comprising an unsaturated compound (D) having a radical polymerizable unsaturated double bond and an unsaturated compound (E) having a hydrolyzable silyl group and a radical polymerizable unsaturated bond. The amount is usually 0.01 to 20% by weight, preferably 0.05 to 10% by weight, relative to 80 to 99.9% 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 component for silver coating in the present invention is a saturated compound (C) having a hydrolyzable silyl group and an unsaturated compound (D) having a radical-polymerizable unsaturated double bond, or An unsaturated compound (E) having a hydrolyzable silyl group and a radical polymerizable unsaturated bond is used as an essential component, and an acrylic polymer (F), a curing catalyst (G),
A photopolymerization initiator (H) is optionally contained.

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

The unsaturated compound (E) 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 (F). . Both methods are effective, but in particular, the saturated compound (C) 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 (E) is an acrylic polymer is effective for improving the adhesion to silver.

In any case, these (C) to (F)
The weight average molecular weight of the radical polymer is 5,000 to 8
It is preferably 00,000. 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 (C34-1) with a silane coupling agent (C34), a silane coupling agent and a radical polymerizing agent. Radical polymer obtained by radically copolymerizing a double bond-containing unsaturated compound (C
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 produce a compound (C31). You can refer to the combination.

Radical Polymer Having Functional Group (C34-1)
Is a radical polymer (C33) 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 (C33-1) described in the method for preparing the radical polymer (C33).

The radical copolymer (D3) having a radical-polymerizable unsaturated double bond is a compound (D31-) having a radical-polymerizable unsaturated double bond in the radical polymer (D31-1) having a functional group. 2) is reacted with (D31) and an unsaturated compound (D32-1) having two or more kinds of unsaturated double bonds with different radical polymerizability is radically polymerized to have a radically reactive group having slow reactivity. There are radical copolymers (D32) and the like.

The combination with the functional group of the compound (D31-2) having a radical-polymerizable unsaturated double bond, which is reacted with the functional group of the radical polymer (D31-1), is a combination of a saturated compound having a functional group and a silane. The combination for producing the compound (C31) obtained by reacting the coupling agent may be referred to.

Examples of the compound (D31-2) having a radical-polymerizable unsaturated double bond that reacts 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 (D31-1) having a functional group is prepared by the same method as the radical polymer (C33) 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 (C33-1) described in the method for preparing the radical polymer (C33). Good. Unsaturated compounds having two or more unsaturated double bonds with different radical polymerizability (D32-
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 (D32-1) 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 (D32-1) having two or more kinds of unsaturated double bonds different in radical polymerizability,
A radical copolymer (D32) having a radical-polymerizable unsaturated double bond can be obtained by using the same method as the radical polymer (C33) in place of the silane coupling agent.

The radical copolymer (E2) 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-polymerizable unsaturated double bond-containing radical copolymer reacted with a compound having a hydrolyzable silyl group such as a silane coupling agent. The method of reacting the radical copolymer with a compound having a hydrolyzable silyl group such as a silane coupling agent may be the same as the method of producing the resin (C3) 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 of producing the unsaturated compound (E) having a hydrolyzable silyl group and a radical polymerizable unsaturated bond may be the same as the method of 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 (C33) and by appropriately selecting and polymerizing a radical copolymer having an effective radical polymerizable unsaturated double bond.

An acrylic copolymer (F) having no hydrolyzable silyl group and a radical-polymerizable unsaturated double bond is prepared in the same manner as the radical polymer (C33), instead of the silane coupling agent. A radical-polymerizable double bond-containing unsaturated compound containing no hydrolyzable silyl group may be used.

Next, the silver deactivator which is important as a compounding ingredient in the composition for silver-coated paint of the present invention is
It is a dicarboxylic acid derivative of mercaptobenzothiazole. Examples of the dicarboxylic acid derivative of 2-mercaptobenzothiazole include certain heterocyclic compounds described as metal corrosion inhibitors in JP-A-61-5069. The substances shown in that patent publication are 2-
A carboxylic acid addition derivative of a heterocyclic compound such as mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole, which is effectively used in the present invention, is (2-benzothiazolylthio) succinic acid. Representative mercapto group hydrogen of 2-mercaptobenzothiazole is an aliphatic dicarboxylic acid,
It is a dicarboxylic acid derivative of mercaptobenzothiazole substituted at its aliphatic carbon position. And the dicarboxylic acid residue constituting this dicarboxylic derivative is not limited to a succinic acid residue, or a malonic acid residue or an anhydride group thereof, or an appropriate substituent such as an ester or an acid amide,
It may contain a group constituting a salt or the like.

The mixing ratio of these metal deactivators is preferably 0.01 to 5% by weight in the coating resin, and particularly preferably 0.5 to 2.0% by weight from the viewpoint of adhesion and hue. When the compounding ratio of the metal deactivator is less than 0.01% by weight, the effect of preventing discoloration (corrosion) on the silver surface is poor, and when it exceeds 5% by weight, a problem of yellowing of the coating film surface occurs, In addition, the adhesion to the silver surface decreases, which is not preferable.

These metal deactivators cooperate well with the above-mentioned various specific resin components, which are the coating substrate components constituting the coating composition of the present invention, to effectively prevent silver corrosion. It turned out for the first time in. It is presumed that the specific resin component probably does not inhibit the action of the specific metal deactivator on the metal surface, and that the specific metal deactivator is dissolved well in the specific resin component.

Other known substances such as metal deactivators and rust preventives do not show the effect as much as these substances, but there are some substances which can be used in combination as required. . Of course, it is also possible to use two or more of the various substances used in the present invention in combination.

In the resin composition of the present invention, in addition to the above-mentioned components, known pigments, dyes, inorganic fillers, organic fillers, and organic fillers, which are well known and commonly used, are used as long as they do not impair 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.

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 balloon, glass balloon.

A halogen group, an epoxy group, an amino group, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zirconate coupling agent, or the like is 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 a 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 tricumyl phenyl 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 a 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 beams, 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 light generators include ultrahigh 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 which is excellent in imparting discoloration resistance (corrosion) are used include lighting equipment, ornaments, electronic materials, semiconductor materials, aerospace materials and a wide variety of 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 used effectively because the effect is large even if it is present.

As a method for coating the silver surface with the coating agent of the present invention which is excellent in imparting discoloration resistance (corrosion), there are, 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. The thickness of the coating film is suitably 3 to 30 μm, and particularly, discoloration resistance (corrosion)
8 to 15 μm is preferable from the viewpoints of the properties and durability.

[0165]

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.

Example 1 100 parts of Acridic A-9540 [manufactured by Dainippon Ink and Chemicals, Inc.] as a reactive group-containing vinyl polymer having a basic nitrogen atom, a hydrolyzable silyl group- and epoxy group-containing compound As Acridic BZ-11
63 [manufactured by Dainippon Ink and Chemicals, Inc.] 15 parts, 2-
As (benzothiazolylthio) -succinic acid, 0.5 parts of Irgacore 252 [manufactured by CIBA-GEIGY], 100 parts of xylene, 30 parts of isopropyl alcohol, and 20 parts of butyl acetate were mixed together to prepare a silicone-acrylic coating agent. Prepared. Then, it is applied on the surface of vapor-deposited silver by a spray method so that the coating film thickness is 8 μm, and the temperature is 70 ° C. and the temperature is 20 ° C.
And dried.

Examples 2 to 3 A vapor-deposited silver film having a cured coating film was obtained in the same manner as in Example 1 except that each raw material was blended in the composition shown in Table 1.

Example 4 As a hydrolyzable silyl group-containing saturated compound, 100 parts of Silacoat SCT-8101 [manufactured by Nissin Corporation],
As a radical-polymerizable unsaturated double bond-containing unsaturated compound Aronix M-215 [Toagosei Co., Ltd.] 2
0 parts, 2.0 parts of Irgacure 184 [manufactured by CIBA-GEIGY] as 1-hydroxycyclohexyl phenyl ketone, 0.5 parts of Irgacore 252 [manufactured by CIBA-GEIGY] as 2- (benzothiazolylthio) -succinic acid, 40 parts of xylene, 60 parts of isopropyl alcohol, and 50 parts of butyl acetate were mixed together to prepare a silicone-acrylic coating agent. Then, the vapor-deposited silver surface was coated by a spray method so that the coating film thickness was 15 μm, and dried at 70 ° C. for 20 minutes. 120w / in the atmosphere
cm high pressure mercury lamp (manufactured by Eye Graphic Co., Ltd.), lamp height 15 cm, conveyor speed 30 m /
Ultraviolet rays were irradiated under the condition of minutes to obtain a vapor-deposited silver film having a cured coating film.

Examples 5 to 6 Vapor-deposited silver films having cured coating films were obtained in the same manner as in Example 4, except that the raw materials were blended in the compositions shown in Table 1.

Comparative Examples 1 to 5 Vapor-deposited silver films having cured coating films were obtained in the same manner as in Example 1 except that the raw materials were mixed in the compositions shown in Table 2.

Comparative Example 6 A vapor-deposited silver film having a cured coating film was obtained in the same manner as in Example 4 except that each raw material was blended in the composition shown in Table 2.

The performance was evaluated by the following tests. The results are shown in Tables 3 and 4.

(1) Adhesion test; cuts are made from the coated surface to reach the vapor-deposited silver surface of the base so that 100 squares of 1.0 mm square can be made, and the cellophane tape is closely adhered to the cut surface and peeled off vigorously. Represents the remaining number of cells.

(2) Humidity resistance test; 40 ° C., relative humidity 95
% Of the sample was left in a constant temperature and humidity chamber (manufactured by Takeda Riken) for 300 hours and then left at room temperature for 24 hours, and the degree of discoloration (corrosion) of the evaporated silver surface was evaluated according to the following four grades.

∙: No discoloration (corrosion) is observed at all ∘: Discoloration (corrosion) is slightly observed Δ: Discoloration (corrosion) is recognized ×: Remarkably discoloration (corrosion) is recognized

(3) Hydrogen sulfide gas resistance test: After leaving the sample for 150 hours in a desiccator in which the hydrogen sulfide gas concentration was adjusted to 20 ppm in an atmosphere of 25 ° C., the adhesion and the deposited silver surface The degree of discoloration (corrosion) was evaluated.

The acrylic vinyl polymers (A-1, A-1 having a reactive group having a basic nitrogen atom in Tables 1 and 2)
A-2), a compound (B) containing a hydrolyzable silyl group and an epoxy group in one molecule, a saturated compound (C) having a hydrolyzable silyl group, an unsaturated group having a radical-polymerizable unsaturated double bond The compound (D), the paint base component other than that in the comparative example, the photopolymerization initiator (H), the silver deactivating component (I), the paint used in Comparative Examples 3 to 6 and the silver deactivator are respectively It is as follows.

A-1: Reactive group vinyl polymer having a basic nitrogen atom Acridic A-9540 [manufactured by Dainippon Ink and Chemicals, Inc.] A-2: Reactive group vinyl having a basic nitrogen atom Polymer Acridic A-9510 [manufactured by Dainippon Ink and Chemicals, Inc.] B-1; Hydrolyzable silyl group and epoxy group-containing compound Acridic BZ-1163 [manufactured by Dainippon Ink and Chemicals, Inc.] C-1; Hydrolyzable silyl group-containing saturated compound Silacoat SCT-810 [manufactured by Nissin Corporation] D-1; Radical-polymerizable unsaturated double bond-containing unsaturated compound Aronix M-215 [Toagosei Co., Ltd. ) Made by the company]

Paint base components other than the above (Comparative Example 4) Acrylic urethane paint; Acridic A-801
[Manufactured by Dainippon Ink and Chemicals, Inc.] / Sumijour
N-75 [Sumitomo Chemical Co., Ltd.] = 100/23
(Weight ratio) Similarly paint base component (Comparative Example 5) Epoxy paint; Epicoat 1001-75X [manufactured by Dainippon Ink and Chemicals, Incorporated] / Tomaide 210 [manufactured by Fuji Kasei Co., Ltd.] = 100/60 (weight ratio)

H-1; 1-hydroxycyclohexyl phenyl ketone Irgacure 184 [manufactured by CIBA-GEIGY] I-1; 2- (benzothiazolylthio) -irgacore 252 succinate [manufactured by CIBA-GEIGY] I-2; Irgamet 39 [manufactured by CIBA-GEIGY] I-3; benzohydrand [manufactured by Tokyo Kasei KK] I-4; benzamide [manufactured by Tokyo Kasei KK]

[0181]

The coating film obtained from the coating agent using the coating composition for silver of the present invention has extremely excellent adhesion and transparency, and also has a moisture resistance and a hydrogen sulfide resistance. Excellent physical properties and excellent durability, and discoloration (corrosion) of silver
It is extremely useful as a protective coating for silver, especially for a silver-deposited surface, which has extremely high preventive properties and long-term durability.

[0182]

[Table 1]

[0183]

[Table 2]

[0184]

[Table 3]

[0185]

[Table 4]

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Claims (11)

[Claims] 1. A coating film substrate component having a hydrolyzable silyl group, a reactive group having a basic nitrogen atom and / or a group having a radical-polymerizable unsaturated double bond, and having a moisture content in the atmosphere at room temperature. In a silver coating composition containing a resin component having curability or curability by active energy rays, a dicarboxylic acid addition derivative (I) of mercaptobenzothiazole (I) as a silver deactivating component is contained in the coating resin. 0.01-5% by weight of the composition for silver coating composition. 2. The room temperature curable resin component has a hydrolyzable silyl group in the acrylic main chain, and forms a siloxane-acryl copolymer by the moisture in the air and cures. The composition according to claim 1, which comprises: 3. The room temperature curable resin component comprises (A) an acrylic vinyl polymer containing a reactive group having a basic nitrogen atom, and (B) a hydrolyzable silyl group and an epoxy group in one molecule. Containing a compound, which contains A component and B
The mixing ratio with the component is such that 1 equivalent of the reactive group contained in the component A is 0.
Composition according to claim 1 or 2, characterized in that it is in the range of 2 to 5 equivalents. 4. The acrylic vinyl polymer (A) is
A polymer obtained by reacting a vinyl-based monomer having at least one group selected from the group consisting of primary amino groups, secondary amino groups, tertiary amino groups, various carboxylic acid amide groups, and cyano groups. 4. The composition according to claim 3, characterized in that 5. The compound (B) is an adduct of γ-glycidoxypropylalkoxysilane and / or γ-glycidoxypropyltriisopropenyloxysilane or γ-isocyanatopropyltriisopropenyloxysilane with glycidol. The composition according to claim 3, which is also an adduct of γ-aminopropyltrimethoxysilane and the like and a diethoxy compound. 6. The composition according to claim 3, wherein the compound (B) is a vinyl polymer having an epoxy group and a hydrolyzable silyl group at the main chain terminal and / or side chain. Stuff. 7. The active energy ray-curable resin component contains a saturated compound (C) having a hydrolyzable silyl group and an unsaturated compound (D) having a radical-polymerizable unsaturated double bond. The composition as described. 8. The active energy ray-curable resin component is 1
Hydrolyzable silyl group and radical polymerizable unsaturated in the molecule 2
The composition according to claim 1, comprising an unsaturated compound (E) having a heavy bond. 9. The composition according to claim 1, wherein the hydrolyzable silyl group is a group represented by the following general formula (1). General formula (1) [Wherein R ₁ represents a hydrogen atom or one organic group consisting of an alkyl group or an aralkyl group, and R ₂ represents a halogen atom or a hydroxyl group, an alkoxy group, an acyloxy group, a phenoxy group, an iminooxy group or an alkenyloxy group. And a is a natural number of 0, 1 or 2. ] 10. Composition according to claim 1, characterized in that the silver coated is a silver-deposited surface. 11. The composition according to any one of claims 1 to 10, wherein the dicarboxylic acid addition derivative (I) of mercaptobenzothiazole is (2-benzothiazolylthio) -succinic acid.