JP2009173718A - Metal-coating material, and light-emitting device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metal-coating material having excellent sulfur barrier properties and transparency, to provide a method for protecting a metal using the metal-coating material, and to provide a light-emitting device capable of affording higher luminance, and prolonging the life. <P>SOLUTION: The metal-coating material includes a polymer (A) obtained by carrying out a hydrolysis-condensation reaction of at least one of silane compound (a1) selected from the group consisting of at least one of organosilane represented by formula (1): R<SP>1</SP><SB>n</SB>Si(OR<SP>2</SP>)<SB>4-n</SB>(1) (wherein, R<SP>1</SP>s represent each a 1-8C monovalent organic group; when two R<SP>1</SP>s are present, the R<SP>1</SP>s may mutually be same or different; R<SP>2</SP>s represent each independently a 1-5C alkyl group or a 1-6C acyl group; and n is an integer of 0-2), a hydrolyzate of the organosilane and a condensate of the organosilane with a polymer (a2) having a silyl group containing a silicon atom bound to a hydrolyzable group and/or a hydroxy group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a metal coating material and a light emitting device.

Metals are used in various articles ranging from daily necessities to electronic parts due to their conductivity and gloss. For example, silver plating is used as an electrode in an LED, and since it also functions as a reflector due to its high reflectance, the role of silver plating for increasing the brightness and extending the life of the LED is significant.

However, the metal is discolored and blackened due to the presence of trace amounts of sulfur and chlorine in the air, and the gloss is lost and the reflectance is lowered. An LED also has a problem of suppressing blackening of silver plating. For example, a light emitting diode in which a protective film is provided on the surface of a metal electrode is known (Patent Document 1). On the other hand, an epoxy resin-based sealing material is known as an LED sealing material. However, although this material is excellent in sulfur barrier property, there is a problem that the epoxy resin itself is discolored when exposed to high temperature in the presence of sulfur. Further, it is pointed out that the silicone-based sealing material is excellent in durability and hardly discolored, but has high gas permeability (for example, Patent Document 2). Therefore, there was a problem that the silver plating was blackened in the presence of sulfur.

An object of the present invention is to provide a metal coating material excellent in sulfur barrier properties and transparency, a metal protection method using the metal coating material, and a light-emitting device capable of achieving high luminance and long life.
JP 2007-109915 A Japanese Patent Laid-Open No. 2004-2784

As a result of earnest research to solve the above problems, the present inventors have found that a polymer obtained from a silane compound and a silyl group-containing polymer is not colored even in a sulfur atmosphere and has excellent sulfur barrier properties. The invention has been completed.

That is, the metal coating material according to the present invention has the following formula (1):
R ¹ nSi (OR ² ) _4-n (1)
(Wherein, R ¹ represents a monovalent organic group having 1 to 8 carbon atoms, optionally .R ² be different be the same as each other, if present two are each independently carbon An alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, n is an integer of 0 to 2)
At least one silane compound (a1) selected from the group consisting of at least one organosilane, a hydrolyzate of the organosilane and a condensate of the organosilane, and a hydrolyzable group and / or Containing a polymer obtained by subjecting a polymer (a2) having a silyl group containing a silicon atom bonded to a hydroxyl group to hydrolysis / condensation reaction (hereinafter also referred to as “organic-inorganic hybrid polymer”) (A). It is characterized by.

The metal coating material according to the present invention comprises the silane compound (a1) and the polymer (a2), the content (Wa1) in terms of a complete hydrolysis condensate of the silane compound (a1), and the polymer (a2). The weight ratio (Wa1 / Wa2) to the solid content (Wa2) is in the range of 5/95 to 95/5 [Wa1 + Wa2 = 100. ] It is preferable that it is an organic inorganic hybrid polymer (A) hydrolyzed and condensed by.

In the metal coating material according to the present invention, in the polymer (a2), the content of a silyl group containing a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group is 0 in terms of the silicon atom content. It is preferable that the organic-inorganic hybrid polymer (A) is 1 to 2% by weight.

This metal coating material may further contain silica particles.

This metal coating material can be preferably used for silver. Moreover, it can use preferably with respect to a silver electrode.

According to the present invention, even when exposed to a sulfur atmosphere, the material itself is not colored, and a metal coating material having excellent sulfur barrier properties can be obtained. In addition, by coating the surface of the silver plating inside the LED with the metal coating material, discoloration of the silver plating when exposed to a sulfur atmosphere can be suppressed, and the life of the LED can be extended.

[Organic inorganic hybrid polymer (A)]
The organic-inorganic hybrid polymer (A) of the present invention is prepared by subjecting a specific silane compound (a1) and a polymer (a2) containing a specific silyl group to a hydrolysis / condensation reaction. More specifically, it is prepared by adding a catalyst for promoting hydrolysis / condensation reaction and water to a mixture containing the silane compound (a1) and the polymer (a2) containing a silyl group.

(Silane compound (a1))
The silane compound (a1) used in the present invention has the following formula (1)
R ¹ _n Si (OR ² ) _4-n (1)
(Wherein, R ¹ represents a monovalent organic group having 1 to 8 carbon atoms, optionally .R ² be different be the same as each other, if present two are each independently carbon An alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, n is an integer of 0 to 2)
At least one silane selected from the group consisting of a hydrolyzate of organosilane (1) and a condensate of organosilane (1) (hereinafter also referred to as “organosilane (1)”) Of these three silane compounds, only one silane compound may be used, any two silane compounds may be mixed, or all three silane compounds may be used. You may mix and use. Moreover, when using organosilane (1) as a silane compound (b1), organosilane (1) may be used individually by 1 type, or may use 2 or more types together. Further, the hydrolyzate and condensate of the organosilane (1) may be formed from one kind of organosilane (1) or may be formed by using two or more kinds of organosilane (1) in combination. Good.

The hydrolyzate of the organosilane (1) is sufficient if at least one of the OR ² groups contained in 2 to 4 of the organosilane (1) is hydrolyzed, for example, one OR ² group. In which two or more OR ² groups are hydrolyzed, or a mixture thereof.

The condensate of the organosilane (1) is formed by condensation of silanol groups in the hydrolyzate produced by hydrolysis of the organosilane (1) to form Si—O—Si bonds. In the present invention, it is not necessary that all of the silanol groups are condensed, and the condensate may be one obtained by condensing a small part of silanol groups, one containing most (including all) silanol groups, These mixtures are also included.

In the above formula (1), R ¹ is a monovalent organic group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group. , I-butyl group, s
ec-butyl group, t-butyl group, n-hexyl group, n-heptyl group, n-octyl group, 2
An alkyl group such as an ethylhexyl group;
Acyl groups such as acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group, caproyl group;
Vinyl group, allyl group, cyclohexyl group, phenyl group, epoxy group, glycidyl group, (
Examples include a (meth) acryloxy group, a ureido group, an amide group, a fluoroacetamide group, and an isocyanate group.

Furthermore, examples of R ¹ include substituted derivatives of the above organic groups. Examples of the substituent of the substituted derivative of R ¹ include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, (
A meth) acryloxy group, a ureido group, an ammonium base, etc. are mentioned. However, the number of carbon atoms of R ¹ composed of these substituted derivatives is preferably 8 or less including the carbon atoms in the substituent. When a plurality of R ¹ are present in the formula (1), they may be the same or different.

As R ² which is an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, n
-Propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-
Can be mentioned pentyl group, R ² is preferably an acyl group having 1 to 6 carbon atoms, for example, an acetyl group, a propionyl group, a butyryl group, valeryl group, etc. caproyl group. When a plurality of R ² are present in the formula (1), they may be the same or different from each other.

Specific examples of such organosilane (1) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane ( N = 0 in formula (1);
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n- Butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxy Silane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-
Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4
-Epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, etc. Trialkoxysilanes (n = 1 in formula (1));
Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxy Silane,
Di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane Di-n-heptyldimethoxysilane, di-n
-Heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, etc. Dialkoxysilanes (n = 2 in formula (1));
Examples thereof include methyltriacetyloxysilane (n = 1 in formula (1)) and dimethyldiacetyloxysilane (n = 2 in formula (1)).

Of these, trifunctional silane compounds in which n = 1 in the formula (1) are mainly used. This trifunctional silane compound is preferably used in combination with a bifunctional silane compound in which n = 2 in formula (1) from the viewpoint of the stability of the organic-inorganic hybrid polymer according to the present invention. As the trifunctional silane compound, trialkoxysilanes are particularly preferable, and as the bifunctional silane compound, dialkoxysilanes are preferable.

When a trifunctional silane compound and a bifunctional silane compound are used in combination, the trifunctional silane compound / 2 bifunctional silane compound is preferably 95 /
5/10/90, more preferably 90 / 10-30 / 70, particularly preferably 85/15
~ 40/60. However, the total of the trifunctional silane compound and the bifunctional silane compound (in terms of complete hydrolysis condensate) is 100. If the content of the trifunctional silane compound is too large, the storage stability of the organic-inorganic hybrid polymer may be inferior. If the content of the trifunctional silane compound is too small, the curability and sulfur barrier property of the cured product may be inferior. . In the present specification, the completely hydrolyzed condensate means a product in which the —OR group of the silane compound is hydrolyzed to 100% to become a SiOH group, and further completely condensed to a siloxane structure.

In the present invention, one type of organosilane (1) may be used alone as the silane compound (a1), but two or more types of organosilane (1) may be used in combination. Silane compound (a1)
When two or more kinds of organosilanes (1) used as the above are averaged and expressed by the above formula (1), the averaged n (hereinafter also referred to as “average value of n”) is preferably 0.5 to 1.9, more preferably 0.6 to 1.7, and particularly preferably 0.7 to 1.5. When the average value of n is less than the above lower limit, the storage stability of the organic-inorganic hybrid polymer may be inferior, and when the upper limit is exceeded, the curability and sulfur barrier property of the cured body (coating film) may be inferior.

The average value of n can be adjusted to the above range by appropriately using a bifunctional to tetrafunctional silane compound and appropriately adjusting the blending ratio.
The same applies to the case where a hydrolyzate or condensate is used as the silane compound (a1).

In the present invention, organosilane (1) may be used as it is as silane compound (a1), but hydrolyzate and / or condensate of organosilane (1) can be used. When the organosilane (1) is used as a hydrolyzate and / or a condensate, it may be prepared by hydrolyzing and condensing the organosilane (1) in advance. When preparing the polymer (A), water is added to hydrolyze and condense the organosilane (1) and water to prepare a hydrolyzate and / or condensate of the organosilane (1). Is preferred.

The condensate of the organosilane (1) is a gel permeation chromatography method (G
The weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) measured by the PC method is preferably 300 to 100,000, more preferably 500 to 50,000.

When the condensate of organosilane (1) is used as the silane compound (a1) in the present invention, it may be prepared from the organosilane (1) or a commercially available condensate of organosilane. Commercially available condensates of organosilane include MKC silicate manufactured by Mitsubishi Chemical Corporation, ethyl silicate manufactured by Colcoat, Toray Dow Corning
Silicone resin made by Silicone Co., Silicone resin made by GE Toshiba Silicone Co., Ltd., silicone resin and silicone oligomer made by Shin-Etsu Chemical Co., Ltd., hydroxyl group-containing polydimethylsiloxane made by Dow Corning Asia Co., Ltd. Examples include silicone oligomers manufactured by Nippon Unicar Co., Ltd. These condensates of commercially available organosilanes may be used as they are or may be further condensed.

(Silyl group-containing polymer (a2))
The polymer (a2) containing a specific silyl group used in the present invention (hereinafter also referred to as “specific silyl group-containing polymer (a2)”) has a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group. Containing silyl groups (hereinafter referred to as “specific silyl groups”). The specific silyl group-containing polymer (a2) preferably has a specific silyl group at the terminal and / or side chain of the polymer molecular chain.

The hydrolyzable group and / or hydroxyl group in the specific silyl group is the silane compound (a1).
The organic-inorganic hybrid polymer (A) is formed by co-condensation with. By coating this organic-inorganic hybrid polymer (A) on the surface of silver plating, the organic-inorganic hybrid polymer (A) is strongly bonded via a siloxane bond, and further, the specific silyl remaining in the organic-inorganic hybrid polymer (A) It is presumed that when the hydrolyzable group and / or hydroxyl group in the group is adsorbed on the silver surface, the sulfur barrier property is exhibited and the silver surface is protected.

The content of the specific silyl group in the specific silyl group-containing polymer (a2) is usually 0.1 to 2% by weight, preferably 0.1 to 2% by weight with respect to the polymer before the introduction of the specific silyl group, in terms of the amount of silicon atoms. 0
. 3 to 1.7% by weight. When the specific silyl group content in the specific silyl group-containing polymer (a2) is less than the above lower limit, the number of specific silyl groups remaining in the covalent bond site with the silane compound (a1) or the metal coating material (A) decreases. The metal surface protection effect may not be obtained. On the other hand, when the above upper limit is exceeded, gelation may occur during storage of the composition.

  The specific silyl group has the following formula (3):

(In the formula, X represents a hydrolyzable group such as a halogen atom, an alkoxyl group, an acetoxy group, a phenoxy group, a thioalkoxyl group, an amino group, or a hydroxyl group; R ⁵ represents a hydrogen atom, 1 carbon atom;
Represents an alkyl group having 10 to 10 carbon atoms or an aralkyl group having 1 to 10 carbon atoms, and i is an integer of 1 to 3; )
It is preferable that it is group represented by these.

Such a specific silyl group-containing polymer (a2) can be produced, for example, by the following methods (I) and (II).
(I) A hydrosilane compound having a specific silyl group represented by the above formula (3) (hereinafter also simply referred to as “hydrosilane compound (I)”) is converted into a vinyl polymer having a carbon-carbon double bond (hereinafter referred to as “hydrosilane compound (I)”). A method of adding the carbon-carbon double bond in the “unsaturated vinyl polymer”).

  (II) The following formula (4)

(Wherein, X, R ^5, i have the same meanings as X, R ^5, i in the formula (3), R6 represents an organic group having a polymerizable double bond)
A silane compound represented by the formula (hereinafter referred to as “unsaturated silane compound (II)”) and another vinyl monomer.

Examples of the hydrosilane compound (I) used in the above method (I) include halogenated silanes such as methyldichlorosilane, trichlorosilane, and phenyldichlorosilane; methyldimethoxysilane, methyldiethoxysilane, and phenyldimethoxy. Alkoxysilanes such as silane, trimethoxysilane, and triethoxysilane; acyloxysilanes such as methyldiacetoxysilane, phenyldiacetoxysilane, and triacetoxysilane;
Examples include aminoxysilanes such as methyldiaminoxysilane, triaminoxysilane, and dimethyl / aminoxysilane. These hydrosilane compounds (I)
These can be used alone or in admixture of two or more.

The unsaturated vinyl polymer used in the method (I) is not particularly limited as long as it is not a polymer having a hydroxyl group. For example, the following methods (I-1) and (I-2) Or it can manufacture by these combinations.

(I-1) A vinyl monomer having a functional group (hereinafter referred to as “functional group (α)”)
After polymerization, the functional group (α) in the (co) polymer is reacted with the functional group (hereinafter referred to as “functional group (β)”) and a carbon / carbon double bond. A method for producing an unsaturated vinyl polymer having a carbon-carbon double bond in a side chain of a polymer molecular chain by reacting an unsaturated compound having:

(I-2) A radical polymerization initiator having a functional group (α) (for example, 4,4′-azobis-4-cyanovaleric acid, etc.) is used, or both the radical polymerization initiator and the chain transfer agent are used. Using a compound having a functional group (α) (for example, 4,4′-azobis-4-cyanovaleric acid and dithioglycolic acid), a vinyl monomer is (co) polymerized to form a polymer molecule After synthesizing a (co) polymer having a functional group (α) derived from a radical polymerization initiator or chain transfer agent at one or both ends of the chain, the functional group (α) in the (co) polymer is synthesized. An unsaturated vinyl polymer having a carbon-carbon double bond at one or both ends of a polymer molecular chain by reacting an unsaturated compound having a functional group (β) and a carbon / carbon double bond. How to manufacture.

Examples of the reaction between the functional group (α) and the functional group (β) in the methods (I-1) and (I-2) include an esterification reaction between a carboxyl group and a hydroxyl group, and a carboxylic anhydride group and a hydroxyl group. Ring-opening esterification reaction, carboxyl group and epoxy group ring-opening esterification reaction, carboxyl group and amino group amidation reaction, carboxylic acid anhydride group and amino group ring-opening amidation reaction, epoxy group Ring-opening addition reaction between a hydroxyl group and an amino group, urethanization reaction between a hydroxyl group and an isocyanate group, a combination of these reactions, and the like.

Examples of vinyl monomers having a functional group (α) include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid; maleic anhydride,
Unsaturated carboxylic acid anhydrides such as itaconic anhydride; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth)
Hydroxyl group-containing vinyl monomers such as acrylate, N-methylol (meth) acrylamide, 2-hydroxyethyl vinyl ether; 2-aminoethyl (meth) acrylate, 2-
Aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 2-
Amino group-containing vinyl monomers such as aminoethyl vinyl ether; 1,1,1-trimethylamine (meth) acrylimide, 1-methyl-1-ethylamine (meth) acrylimide, 1,1-dimethyl-1- (2 -Hydroxypropyl) amine (meth) acrylimide, 1,1-dimethyl-1- (2'-phenyl-2'-hydroxyethyl) amine (meth)
Aminimide group-containing vinyl monomers such as acrylimide, 1,1-dimethyl-1- (2′-hydroxy-2′-phenoxypropyl) amine (meth) acrylimide; glycidyl (meth) acrylate, allyl glycidyl ether, etc. And epoxy group-containing vinyl monomers. These vinyl monomers having a functional group (α) can be used alone or in admixture of two or more.

Examples of other vinyl monomers copolymerizable with the vinyl monomer having a functional group (α) include styrene, α-methyl styrene, 4-methyl styrene, 2-methyl styrene, 3
-Methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 4-ethylstyrene, 4-ethoxystyrene, 3,4-dimethylstyrene, 3,4-diethylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4 -Chloro-3-methylstyrene, 4-
aromatic vinyl monomers such as t-butylstyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene, 1-vinylnaphthalene;
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, amyl (
(Meth) acrylate compounds such as (meth) acrylate, i-amyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, cyclohexyl methacrylate;
Divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) ) Acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra ( Polyfunctional monomers such as (meth) acrylates;
(Meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N′-methylenebisacrylamide, diacetone acrylamide, maleic acid amide, maleimide, etc. Acid amide compounds of
Vinyl compounds such as vinyl chloride, vinylidene chloride and fatty acid vinyl esters;
1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-
Substituted by substituents such as butadiene, 2-neopentyl-1,3-butadiene, 2-chloro-1,3-butadiene, 2-cyano-1,3-butadiene, isoprene, alkyl groups, halogen atoms, cyano groups Substituted aliphatic conjugated dienes such as substituted linear conjugated pentadienes, linear and side chain conjugated hexadienes;
Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile;
Fluorine atom-containing monomers such as trifluoroethyl (meth) acrylate and pentadecafluorooctyl (meth) acrylate;
4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (
Piperidine monomers such as (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine;
2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methacryloxyethylphenyl) -2H-benzotriazole UV-absorbing monomers such as 2-hydroxy-4- (methacryloyloxyethoxy) benzophenone and 2-hydroxy-4- (acryloyloxyethoxy) benzophenone;
Examples include dicaprolactone. These can be used alone or in combination of two or more.

As an unsaturated compound having a functional group (β) and a carbon / carbon double bond, for example, a vinyl monomer similar to the vinyl monomer having a functional group (α), or the above hydroxyl group-containing vinyl type An isocyanate group-containing unsaturated compound obtained by reacting a monomer and a diisocyanate compound in an equimolar amount can be exemplified.

Moreover, as unsaturated silane compound (II) used for the method of said (II),
_{CH 2 = CHSi (CH 3)} (OCH 3) 2, CH 2 = CHSi (OCH 3) 3,
CH ₂ = CHSi (CH ₃ ) Cl ₂ , CH ₂ = CHSiCl ₃ ,
_{CH 2 = CHCOO (CH 2)} 2 Si (CH 3) (OCH 3) 2,
_{CH 2 = CHCOO (CH 2)} 2 Si (OCH 3) 3,
_{CH 2 = CHCOO (CH 2)} 3 Si (CH 3) (OCH 3) 2,
CH ₂ = CHCOO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,
CH ₂ = CHCOO (CH ₂ ) ₂ Si (CH ₃ ) Cl ₂ , CH ₃
CH ₂ = CHCOO (CH ₂ ) ₂ SiCl ₃ ,
CH ₂ = CHCOO (CH ₂ ) ₃ Si (CH ₃ ) Cl ₂ ,
CH ₂ = CHCOO (CH ₂ ) ₃ SiCl ₃ ,
_{CH 2 = C (CH 3)} COO (CH 2) 2 Si (CH 3) (OCH 3) 2,
_{CH 2 = C (CH 3)} COO (CH 2) 2 Si (OCH 3) 3,
_{CH 2 = C (CH 3)} COO (CH 2) 3 Si (CH 3) (OCH 3) 2,
_{CH 2 = C (CH 3)} COO (CH 2) 3 Si (OCH 3) 3,
_{CH 2 = C (CH 3)} COO (CH 2) 2 Si (CH 3) Cl 2,
CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₂ SiCl ₃ ,
_{CH 2 = C (CH 3)} COO (CH 2) 3 Si (CH 3) Cl 2,
_{CH 2 = C (CH 3)} COO (CH 2) 3 SiCl 3,

Can be mentioned. These can be used alone or in combination of two or more.
Examples of other vinyl monomers copolymerized with the unsaturated silane compound include, for example, vinyl monomers having the functional group (α) exemplified in the method (I-1) and other vinyl monomers. A monomer etc. can be mentioned.

Examples of the method for producing the specific silyl group-containing polymer (a2) include, for example, a method in which each monomer is added at once and polymerized, and after the polymerization of a part of the monomer, the remainder is continuously obtained. Or the method of adding and polymerizing intermittently, the method of adding a monomer continuously from the time of a polymerization start, etc. are mentioned. These polymerization methods may be combined.

A preferred polymerization method includes solution polymerization. The solvent used in the solution polymerization is not particularly limited as long as it can produce the specific silyl group-containing polymer (a2). For example, alcohols, aromatic hydrocarbons, ethers, ketones, esters, etc. Can be mentioned. Examples of the alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, t
-Butyl alcohol, n-hexyl alcohol, n-octyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene monomethyl ether acetate, And diacetone alcohol. Aromatic hydrocarbons include benzene, toluene, xylene, etc., ethers include tetrahydrofuran, dioxane, etc., and ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and the like. Examples of esters include ethyl acetate, propyl acetate, butyl acetate, propylene carbonate, methyl lactate,
Examples include ethyl lactate, normal propyl lactate, isopropyl lactate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and the like. These organic solvents may be used individually by 1 type, or 2 or more types may be mixed and used for them.

Moreover, in the said superposition | polymerization, a well-known thing can be used for a polymerization initiator, a molecular weight modifier, a chelating agent, and an inorganic electrolyte.
In the present invention, as the specific silyl group-containing polymer (a2), in addition to the specific silyl group-containing polymer polymerized as described above, other specific silyl group-containing epoxy resins, specific silyl group-containing polyester resins and the like are used. A specific silyl group-containing polymer can also be used. Examples of the specific silyl group-containing epoxy resin include bisphenol A type epoxy resin and bisphenol F.
Type epoxy resin, hydrogenated bisphenol A type epoxy resin, aliphatic polyglycidyl ether, aliphatic polyglycidyl ester, and other epoxy resins having a specific silyl group as an amino silane, vinyl silane, carboxy silane, glycidyl silane It can be produced by reacting a kind or the like. The specific silyl group-containing polyester resin is produced, for example, by reacting a carboxyl group or a hydroxyl group contained in the polyester resin with aminosilanes, carboxysilanes, glycidylsilanes or the like having a specific silyl group. Can do.

The Mw in terms of polystyrene measured by the GPC method of the specific silyl group-containing polymer (a2) is preferably 2,000 to 100,000, more preferably 3,000 to 50,000.
It is.

In the present invention, the specific silyl group-containing polymer (a2) can be used alone or in admixture of two or more.
(catalyst)
In the present invention, in order to promote the hydrolysis / condensation reaction of the silane compound (a1) and the specific silyl group-containing polymer (a2), the silane compound (a1) and the specific silyl group-containing polymer (a2) It is preferred to add a catalyst to the mixture. By adding a catalyst, the degree of crosslinking of the resulting organic-inorganic hybrid polymer (A) can be increased, and the molecular weight of the polysiloxane produced by the polycondensation reaction of the organosilane (1) is increased, resulting in strength. In addition, a cured product excellent in long-term durability can be obtained, and the sulfur barrier property when coated on the silver surface is also increased. Furthermore, the addition of the catalyst promotes the reaction between the silane compound (a1) and the specific silyl group-containing polymer (a2), and sufficient reaction sites (alkoxy groups) are formed in the organic-inorganic hybrid polymer (A). . When this organic / inorganic hybrid polymer (A) is coated on a silver plating and cured, a metal coating layer with a high siloxane bond and a high crosslink density is formed, and a sulfur barrier property is exhibited. It is estimated that the discoloration of can be protected.

As a catalyst used for promoting such hydrolysis / condensation reaction, for example,
Examples include basic compounds, acidic compounds, salt compounds, and metal chelate compounds.
(Basic compound)
Examples of the basic compound include ammonia (including ammonia aqueous solution), organic amine compounds, alkali metals such as sodium hydroxide and potassium hydroxide, hydroxides of alkaline earth metals, alkalis such as sodium methoxide and sodium ethoxide. Examples thereof include metal alkoxides. Of these, ammonia and organic amine compounds are preferred.

Examples of the organic amine include alkylamine, alkoxyamine, alkanolamine, and arylamine.
Alkylamines include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine , Alkylamines having an alkyl group having 1 to 4 carbon atoms, such as triethylamine, tripropylamine, and tributylamine.

Alkoxyamines include methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, propoxymethylamine, propoxyethylamine, propoxypropylamine, propoxybutylamine, butoxymethylamine , Alkoxyamines having 1 to 4 carbon atoms such as butoxyethylamine, butoxypropylamine, and butoxybutylamine.

Examples of the alkanolamine include methanolamine, ethanolamine, propanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanolamine,
N-propylmethanolamine, N-butylmethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N-methylpropanolamine, N-ethylpropanolamine, N- Propylpropanolamine, N-butylpropanolamine, N-methylbutanolamine, N-ethylbutanolamine, N-propylbutanolamine, N-butylbutanolamine, N, N-dimethylmethanolamine, N, N-diethylmethanolamine, N,
N-dipropylmethanolamine, N, N-dibutylmethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dipropylethanolamine, N, N-dibutylethanolamine, N, N-dimethylpropanolamine,
N, N-diethylpropanolamine, N, N-dipropylpropanolamine, N, N
-Dibutylpropanolamine, N, N-dimethylbutanolamine, N, N-diethylbutanolamine, N, N-dipropylbutanolamine, N, N-dibutylbutanolamine, N-methyldimethanolamine, N-ethyldimethanol Amine, N-propyldimethanolamine, N-butyldimethanolamine, N-methyldimethanolamine,
N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, N-methyldipropanolamine, N-ethyldipropanolamine, N-
Propyldipropanolamine, N-butyldipropanolamine, N-methyldibutanolamine, N-ethyldibutanolamine, N-propyldibutanolamine, N-butyldibutanolamine, N- (aminomethyl) methanolamine, N -(Aminomethyl) ethanolamine, N- (aminomethyl) propanolamine, N- (aminomethyl)
Butanolamine, N- (aminoethyl) methanolamine, N- (aminoethyl) ethanolamine, N- (aminoethyl) propanolamine, N- (aminoethyl) butanolamine, N- (aminopropyl) methanolamine, N- (Aminopropyl) ethanolamine, N- (aminopropyl) propanolamine, N- (aminopropyl) butanolamine, N- (aminobutyl) methanolamine, N- (aminobutyl) ethanolamine, N- (aminobutyl) propanol Examples thereof include alkanolamines having an alkyl group having 1 to 4 carbon atoms such as amine and N- (aminobutyl) butanolamine.

Examples of the arylamine include aniline and N-methylaniline.
Furthermore, as an organic amine other than the above, tetramethylammonium hydroxide,
Tetraalkylammonium hydroxide such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide; tetraalkylethylenediamine such as tetramethylethylenediamine, tetraethylethylenediamine, tetrapropylethylenediamine, tetrabutylethylenediamine; methylamino Methylamine, methylaminoethylamine, methylaminopropylamine, methylaminobutylamine, ethylaminomethylamine, ethylaminoethylamine, ethylaminopropylamine, ethylaminobutylamine, propylaminomethylamine, propylaminoethylamine, propylaminopropylamine, propylamino Butylamine, butyl Mino methylamine, butyl ethylamine, butyl aminopropylamine, alkylaminoalkyl amines such butylamino tributylamine;
Polyamines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-phenylenediamine, p-phenylenediamine; pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, morpholine, methylmorpholine, diazabicyclo Okran, diazabicyclononane,
Diazabicycloundecene is also included.

Such basic compounds may be used alone or in combination of two or more.
Of these, triethylamine, tetramethylammonium hydroxide, and pyridine are particularly preferable.

(Acidic compounds)
Examples of the acidic compound include organic acids and inorganic acids. Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, maleic anhydride, methylmalonic acid, adipic acid, Sebacic acid, gallic acid, butyric acid, meritic acid, arachidonic acid, mikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfone Examples include acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, methanesulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

Such acidic compounds may be used alone or in combination of two or more. Of these, maleic acid, maleic anhydride, methanesulfonic acid, and acetic acid are particularly preferred.
(Salt compound)
Examples of the salt compound include naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate, and alkali metal salts such as carbonic acid.

(Metal chelate compound)
Examples of the metal chelate compound include organometallic compounds and / or partial hydrolysates thereof (hereinafter, organometallic compounds and / or partial hydrolysates thereof are collectively referred to as “organometallic compounds”).

Examples of the organometallic compounds include the following formula (b):
M (OR ⁷ ) _r (R ⁸ COCHCOR ⁹ ) _s (b)
(Wherein M represents at least one metal atom selected from the group consisting of zirconium, titanium and aluminum, and R ⁷ and ⁸ are each independently a methyl group, an ethyl group, an n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group,
represents a monovalent hydrocarbon group having 1 to 6 carbon atoms such as an n-pentyl group, n-hexyl group, cyclohexyl group, and phenyl group, and R ⁹ represents the monovalent hydrocarbon having 1 to 6 carbon atoms. Group or
Methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, se
represents an alkoxyl group having 1 to 16 carbon atoms such as a c-butoxy group, a t-butoxy group, a lauryloxy group, and a stearyloxy group, and r and s are each independently an integer of 0 to 4, and (r + s ) = (M valence satisfied))
(Hereinafter referred to as “organometallic compound (b)”),
A tetravalent tin organometallic compound in which one or two alkyl groups having 1 to 10 carbon atoms are bonded to one tin atom (hereinafter referred to as “organotin compound”), or
These partial hydrolysates are exemplified.

Further, as organometallic compounds, tetraalkoxytitanium such as tetramethoxytitanium, tetraethoxytitanium, tetra-i-propoxytitanium, tetra-n-butoxytitanium; methyltrimethoxysilane, ethyltriethoxysilane, n-propyltri Methoxysilane, i-propyltriethoxysilane, n-hexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane 3- (2-aminoethyl) -aminopropyltrimethoxysilane, 3- (2-aminoethyl) -aminopropyltriethoxysilane, 3- (2-aminoethyl) -aminopropylmethyldimethoxysila , 3-anilino trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-isocyanate propyl trimethoxysilane,
Trialkoxysilanes such as 3-glycidoxypropyltriethoxysilane and 3-ureidopropyltrimethoxysilane; dimethyldiethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-i-propyldiethoxysilane , Di-n-
Titanium alcoholates such as dialkoxysilanes such as pentyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, diphenyldimethoxysilane, and condensates thereof can be used.

Examples of the organometallic compound (b) include tetra-n-butoxyzirconium, tri-
n-butoxy ethyl acetoacetate zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, n-butoxy tris (ethyl acetoacetate) zirconium, tetrakis (n-propyl acetoacetate) zirconium, tetrakis (
Organic zirconium compounds such as acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, di-n-butoxy bis (acetylacetonato) zirconium;
Tetra-i-propoxy titanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy bis (acetylacetate) titanium, di-
organotitanium compounds such as i-propoxy bis (acetylacetone) titanium;
Tri-i-propoxyaluminum, di-i-propoxyethyl acetoacetate aluminum, di-i-propoxy acetylacetonate aluminum, i-propoxy bis (ethylacetoacetate) aluminum, i-propoxy bis (acetylacetonate) And organoaluminum compounds such as aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonatobis (ethylacetoacetate) aluminum.

  As an organic tin compound, for example,

Carboxylic acid type organotin compounds such as;

Mercaptide-type organotin compounds such as

Sulfide-type organotin compounds such as;

Chloride-type organotin compounds such as;
Reaction of organotin oxides such as (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO, and ester compounds such as silicates, dimethyl maleate, diethyl maleate and dioctyl phthalate Product;
Etc.

Such metal chelate compounds may be used singly or in combination of two or more. Of these, di-n-butoxy bis (acetylacetonato) zirconium, di-i-propoxy bis (acetylacetonato) titanium, di-i-propoxyethylacetoacetate aluminum, tris (ethylacetoacetate) aluminum Or these partial hydrolysates are preferable.

Moreover, the said catalyst can also be used in mixture with a zinc compound and another reaction retarder.
When the catalyst is other than the organometallic compound, the amount of the catalyst used is the silane compound (a
1) Usually 0 with respect to 100 parts by weight (in terms of complete hydrolysis condensate of organosilane (1))
. 001 to 100 parts by weight, preferably 0.01 to 80 parts by weight, more preferably 0.1 to 100 parts by weight
50 parts by weight. When the catalyst is an organometallic compound, the silane compound (a1) 10
The amount is usually 100 parts by weight or less, preferably 0.1 to 80 parts by weight, more preferably 0.5 to 50 parts by weight with respect to 0 part by weight (in terms of complete hydrolysis condensate of organosilane (1)).
When the usage-amount of the said catalyst exceeds the said upper limit, it gelatinizes by the fall of the storage stability of an organic inorganic hybrid polymer, or the crosslinking degree of a metal coating layer becomes high too much, and a crack may generate | occur | produce.

(water)
In the present invention, water is added to the mixture of the silane compound (a1) and the specific silyl group-containing polymer (a2) to co-condense the silane compound (a1) and the specific silyl group-containing polymer (a2). It is preferable to prepare the organic-inorganic hybrid polymer (A).

The amount of water added at this time is usually 0.1 to 1.0 mol, preferably 0.2 to 0.8 mol, based on 1 mol of all OR ² groups in the silane compound (a1). More preferably, 0.
25-0.6 mol. When the amount of water added is in the above range, gelation hardly occurs, and the composition exhibits good storage stability. Moreover, when the amount of water added is in the above range, a sufficiently cross-linked metal coating material (A) is obtained. By using a composition containing such an organic-inorganic hybrid polymer (A), sulfur barrier properties and metal A metal coat layer having excellent surface protection can be obtained.

(Organic solvent)
In the present invention, the silane compound (a1) and the specific silyl group-containing polymer (a2) may be subjected to a hydrolysis / condensation reaction in an organic solvent. At this time, the organic solvent used at the time of preparation of the silyl group-containing polymer (a2) can be used as it is. Moreover, in order to adjust the solid content density | concentration at the time of metal coating material (A) preparation, an organic solvent can also be added as needed. Furthermore, the organic solvent used in the preparation of the silyl group-containing polymer (a2) may be removed, and a new organic solvent may be added.

  The amount of the organic solvent is such that the solid content concentration during the preparation of the organic-inorganic hybrid polymer (A) is preferably in the range of 10 to 60% by weight, more preferably 15 to 50% by weight, and particularly preferably 20 to 40% by weight. Can be added. When the organic solvent used in the preparation of the silyl group-containing polymer (a2) is used as it is and the solid content concentration in the preparation of the organic-inorganic hybrid polymer (A) is in the above range, the organic solvent is added. However, it may not be added.

The reactivity of the silane compound (a1) and the specific silyl group-containing polymer (a2) can be controlled by adjusting the solid content concentration when preparing the organic-inorganic hybrid polymer (A). When the solid content concentration at the time of preparing the organic-inorganic hybrid polymer (A) is less than the lower limit, the reactivity between the silane compound (a1) and the specific silyl group-containing polymer (a2) may be lowered. If the solid content concentration during the preparation of the organic-inorganic hybrid polymer (A) exceeds the upper limit, gelation may occur. In addition, the amount of solid content in solid content concentration said here is the usage-amount (Wa1) of conversion of the complete hydrolysis-condensation product of a silane compound (a1) and the usage-amount (Wa2) of solid content conversion of a specific silyl group containing polymer (a2). ).

The organic solvent is not particularly limited as long as the above components can be mixed uniformly. The alcohols and aromatic hydrocarbons exemplified as the organic solvent used for the production of the specific silyl group-containing polymer (a2). And ethers, ketones, esters and the like. Moreover, these organic solvents may be used individually by 1 type, or may mix and use 2 or more types.

(Stability improver)
In the present invention, in order to improve the storage stability of the organic-inorganic hybrid polymer (A), it is preferable to add a stability improver as necessary after preparing the organic-inorganic hybrid polymer (A). The stability improver used in the present invention is represented by the following formula (6).
R ¹⁰ COCH ₂ COR ¹¹ (6)
(In the formula, R ¹⁰ represents methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group) Represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, such as a group or a phenyl group, and R ¹¹ represents the carbon number 1
To 6 monovalent hydrocarbon groups, or a methoxy group, an ethoxy group, an n-propoxy group, i-
An alkoxyl group having 1 to 16 carbon atoms such as propoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, lauryloxy group and stearyloxy group is represented. )
At least one selected from the group consisting of β-diketones, β-ketoesters, carboxylic acid compounds, dihydroxy compounds, amine compounds and oxyaldehyde compounds
A kind of compound.

When organometallic compounds are used as the catalyst, it is preferable to add a stability improver represented by the above formula (6). By using the stability improver, the stability improver coordinates to the metal atom of the organometallic compound, and this coordination is excessive between the silane compound (a1) and the specific silyl group-containing polymer (a2). It is considered that the co-condensation reaction can be suppressed and the storage stability of the obtained organic-inorganic hybrid polymer (A) can be further improved.

Examples of such stability improvers include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-
n-butyl, acetoacetate-sec-butyl, acetoacetate-t-butyl, hexane-2,4
-Dione, heptane-2,4-dione, heptane-3,5-dione, octane-2,4-
Dione, nonane-2,4-dione, 5-methylhexane-2,4-dione, malonic acid, oxalic acid, phthalic acid, glycolic acid, salicylic acid, aminoacetic acid, iminoacetic acid, ethylenediaminetetraacetic acid, glycol, catechol, ethylenediamine 2,2-bipyridine, 1,1
Examples include 0-phenanthroline, diethylenetriamine, 2-ethanolamine, dimethylglyoxime, dithizone, methionine, and salicylaldehyde. Of these,
Acetylacetone and ethyl acetoacetate are preferred.

Moreover, a stability improver may be used individually by 1 type, or 2 or more types may be mixed and used for it.
The amount of the stability improver used in the present invention is usually 2 moles or more, preferably 3 to 20 moles per mole of the organometallic compound of the organometallic compounds. If the amount of the stability improver is less than the above lower limit, the effect of improving the storage stability of the resulting composition may be insufficient.

(Preparation method of organic-inorganic hybrid polymer (A))
The organic-inorganic hybrid polymer (A) of the present invention can be prepared by co-condensing the silane compound (a1) and the specific silyl group-containing polymer (a2). Particularly preferably, it can be prepared by adding a catalyst for hydrolysis / condensation reaction and water and co-condensing the mixture of the silane compound (a1) and the specific silyl group-containing polymer (a2).

At this time, the content (Wa1) of the silane compound (a1) and the specific silyl group-containing polymer (a2)
The weight ratio (Wa1 / Wa2) to the content (Wa2) is 5/95 to 95/5, preferably 15/85 to 85/15, where Wa1 + Wa2 = 100. Wa1
Is the complete hydrolysis condensate conversion value of the silane compound (a1), and Wa2 is the solid content conversion value of the specific silyl group-containing polymer (a2). When the weight ratio (Wa1 / Wa2) is in the above range, a cured product having excellent transparency and weather resistance can be obtained.

Specifically, the organic-inorganic hybrid polymer (A) is preferably prepared by the following methods (1) to (3).
(1) Water in the above range is added to a mixed solution of the silane compound (a1), the specific silyl group-containing polymer (a2) and the hydrolysis / condensation reaction catalyst, and the temperature is 40 to 80 ° C., the reaction time. 0.5 ~
Co-condensation of the silane compound (a1) and the specific silyl group-containing polymer (a2) in 12 hours,
An organic-inorganic hybrid polymer (A) is prepared. Thereafter, if necessary, other additives such as a stability improver may be added.

  (2) Water in the above range is added to the silane compound (a1), and the hydrolysis / condensation reaction of the silane compound (a1) is performed at a temperature of 40 to 80 ° C. for 0.5 to 12 hours. Next, the specific silyl group-containing polymer (b2) and the catalyst for hydrolysis / condensation reaction are added and mixed, and further subjected to a condensation reaction at a temperature of 40 to 80 ° C. and a reaction time of 0.5 to 12 hours. Prepare (A). Thereafter, if necessary, other additives such as a stability improver may be added.

When a metal chelate compound is used as the hydrolysis condensation catalyst, it is preferable to add the above stability improver after the reaction.
The weight average molecular weight of the organic-inorganic hybrid polymer (A) obtained by the above method is usually 3,000 to 200,000, preferably 4,000 to 150,000, in terms of polystyrene measured by gel permeation chromatography. Preferably it is 5,000-100,000.

〔silica〕
The metal coating material of the present invention may further contain silica particles (B).
When the silica particles (B) are blended, they can be used in the form of powder or a solvent-based sol or colloid dispersed in a polar solvent such as isopropyl alcohol or a nonpolar solvent such as toluene. In order to improve the dispersibility of the silica particles (B), a surface treatment may be performed.
The primary particle diameter of these silica particles (B) is usually 0.0001 to 1 μm, more preferably 0.001 to 0.5 μm, and particularly preferably 0.002 to 0.2 μm.
In the case of a silica particle solvent-based sol or colloid, the solid content concentration is usually more than 0% by weight and 50% by weight or less, preferably 0.01% by weight or more and 40% by weight or less.
In the present invention, as surface-treated untreated powdered silica, # 150, # 200, # 300 manufactured by Nippon Aerosil Co., Ltd., and as hydrophobized powdered silica, R972, R974, R976, RX200 manufactured by Nippon Aerosil Co., Ltd. , RX300, RY200S, RY300, R106, SS50A manufactured by Tosoh Corporation, Fuji Silicia's Silo Hovic 100, and the like.
Examples of the solvent-dispersed colloidal silica include alcohol-based solvent-dispersed colloidal silica such as isopropyl alcohol manufactured by Nissan Chemical Industries, ketone-based solvent-dispersed colloidal silica such as methylisobutyl, and nonpolar solvent-dispersed colloidal silica such as toluene. It is done. Silica particles (B) may be added during the preparation of the organic-inorganic hybrid polymer (A), or may be added after the preparation of the organic-inorganic hybrid polymer (A).
The amount of silica particles (B) used is usually more than 0% by weight and 80% by weight or less, preferably 5% by weight or more and 50% by weight or less in terms of solids, based on the solids of the organic-inorganic hybrid polymer (A). It is.

[Light emitting device]
A light emitting device can be obtained by using a plated member or a metal electrode which is coated and cured with the metal coating material of the present invention. 1-3 schematically show a light emitting device. As the LED element, a blue LED element, a white LED element, an ultraviolet LED element, or the like can be used. Furthermore, a phosphor can be contained in the metal coat layer to convert light emitted from the LED element. Further, the sealing member can be coated with the metal coating material of the present invention to protect it from sulfur or the like.

[Metal protection method]
By coating the metal with the metal coating material of the present invention, the metal can be protected from discoloration and the like. The composition of the coating material, the coating method, and the like are as described above.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. In the examples and comparative examples, “parts” and “%” indicate “parts by weight” and “% by weight” unless otherwise specified. In addition, various measurements in Examples and Comparative Examples were performed by the following methods.

(1) GPC measurement The weight average molecular weight of siloxane was measured by gel permeation chromatography under the following conditions, and was shown as a polystyrene equivalent value. Apparatus: HLC-8120C (manufactured by Tosoh Corporation) Column: TSK-gel Multipore HXL-M (manufactured by Tosoh Corporation) Eluent: THF, flow rate 0.5 mL / min, load 5.0%, 100 μL
(2) Storage stability The obtained composition was sealed in a polyethylene container at room temperature for 1 month, and the presence or absence of gelation was visually determined. About the thing which is not gelatinized, the viscosity was measured at 25 degreeC with the BM type | mold viscosity meter by Tokyo Keiki Co., Ltd., and the following reference | standard evaluated. A: Viscosity change rate before and after storage is 20% or less, B: Viscosity change rate before and after storage exceeds 20% (3) Stability under sulfur exposure 0.06 g of iron sulfide and 0 in a pressure-resistant container with a capacity of 150 cm ³ After mixing 20 g of 47% by weight of sulfuric acid solution, a cured product having a thickness of 100 μm and a size of 5 mm square prepared under predetermined curing conditions was immediately charged in the pressure vessel and sealed (theoretical concentration of hydrogen sulfide 10 vol%). The pressure vessel was heated at 120 ° C. for 5 hours and then cooled, the cured product was taken out, the appearance of silver plating was observed, and the following criteria were evaluated.
A: No change C: Discolored to brown

(4) Silver blackening suppression ability After mixing 0.06 g of iron sulfide and 0.20 g of sulfuric acid in a pressure vessel with a capacity of 150 cm ^3, a silver blackening suppression ability evaluation sample was immediately charged and sealed (the theory of hydrogen sulfide). Concentration 10 vol%). The pressure vessel was heated at 120 ° C. for 5 hours and then cooled, the test sample was taken out, the appearance of silver plating was observed, and evaluated according to the following criteria.
A: No change B: Slight color change C: Black color change

[Preparation of specific silyl group-containing polymer (a2)]
<Preparation Example 1-1>
In a reactor equipped with a reflux condenser and a stirrer, 55 parts of methyl methacrylate, 5 parts of 2-ethylhexyl acrylate, 5 parts of cyclohexyl methacrylate, 10 parts of γ-methacryloxypropyltrimethoxysilane, 20 parts of glycidyl methacrylate, 4- (meth) After adding and mixing 5 parts of acryloyloxy-2,2,6,6-tetramethylpiperidine, 75 parts of i-butyl alcohol, 50 parts of methyl ethyl ketone and 25 parts of methanol, the mixture was heated to 80 ° C. with stirring. A solution prepared by dissolving 3 parts of azobisisovaleronitrile in 8 parts of xylene was added dropwise to this mixture over 30 minutes, and then reacted at 80 ° C. for 5 hours. After cooling, 36 parts of methyl ethyl ketone was added, and a specific silyl group-containing polymer (a2-) having a solid content concentration of 35%, Mw measured by GPC method of 12,000, and silicon content in the solid content of 1.1% by weight. A solution containing 1) was obtained.

<Preparation Example 1-2>
The solid content concentration was 35%, Mw was 13,000, and the silicon content in the solid content was the same as in Preparation Example 1-1 except that 20 parts of 2-hydroxyethyl methacrylate was used instead of 20 parts of glycidyl methacrylate. A solution containing 1.1 wt% of the specific silyl group-containing polymer (a2-2) was obtained.

<Preparation Example 1-3>
In a reactor equipped with a reflux condenser and a stirrer, 30 parts of methyl methacrylate, 10 parts of n-butyl acrylate, 10 parts of γ-methacryloxypropyltrimethoxysilane, 20 parts of glycidyl methacrylate, 4- (meth) acryloyloxy-2, 2,6,6-tetramethylpiperidine 10 parts, 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole 20 parts, i-butyl alcohol 75 parts, methyl ethyl ketone 50 parts and methanol 25 parts After mixing, the mixture was heated to 80 ° C. with stirring. A solution prepared by dissolving 4 parts of azobisisovaleronitrile in 10 parts of xylene was added dropwise to this mixture over 30 minutes, and then reacted at 80 ° C. for 5 hours. After cooling, 83 parts of methyl ethyl ketone was added, and a specific silyl group-containing polymer (a2-) having a solid content concentration of 30%, an Mw measured by GPC method of 10,000, and a silicon content in the solid content of 1.1% by weight. A solution containing 3) was obtained.

<Preparation Example 1-4>
In a reactor equipped with a reflux condenser and a stirrer, 70 parts of methyl methacrylate, 10 parts of 2-ethylhexyl acrylate, 5 parts of cyclohexyl methacrylate, 10 parts of γ-methacryloxypropyltrimethoxysilane, 4- (meth) acryloyloxy-2, After adding 5 parts of 2,6,6-tetramethylpiperidine, 75 parts of i-butyl alcohol, 50 parts of methyl ethyl ketone and 25 parts of methanol, the mixture was heated to 80 ° C. with stirring. A solution prepared by dissolving 3 parts of azobisisovaleronitrile in 8 parts of xylene was added dropwise to this mixture over 30 minutes, and then reacted at 80 ° C. for 5 hours. After cooling, 35 parts of methyl ethyl ketone was added, and a specific silyl group-containing polymer (a2-) having a solid content concentration of 35%, Mw measured by GPC method of 12,000, and silicon content in the solid content of 1.1% by weight. 4) A solution was obtained.

[Preparation of the composition of the present invention]
<Example 1>
In a reactor equipped with a stirrer and a reflux condenser, 24 parts of methyltrimethoxysilane and 10 parts of dimethyldimethoxysilane as the silane compound (a1) and the above-mentioned specific silyl group-containing polymer (a2) as the specific silyl group-containing polymer (a2) 118 parts of a solution containing a2-1), 10 parts of i-propyl alcohol as an organic solvent, and 2 parts of i-propyl alcohol 75% diluted solution of di-i-propoxy-ethylacetoacetate aluminum as a hydrolysis / condensation reaction catalyst In addition, the mixture was mixed and heated to 50 ° C. with stirring. 6 parts of water (corresponding to 0.48 mol with respect to 1 mol of all OR ² groups in the silane compound (a1)) was dropped into this over 30 minutes, followed by reaction at 60 ° C. for 4 hours, GPC method The composition (A-1) of this invention containing the organic-inorganic hybrid polymer whose Mw measured by 13,000 was obtained. Thereafter, 2 parts of acetylacetone as a stability improver was added and stirred for 1 hour, then cooled to room temperature, and 129 parts of methyl isobutyl ketone as a diluent solvent was added to adjust the solid content concentration to 20% by weight. As a result of evaluating the storage stability, it was A.

<Examples 2 to 4>
A solution containing the compositions (A-2) to (A-4) of the present invention (all with a solid content concentration of 20% by weight) in the same manner as in Example 1, except that each component was changed to the components shown in Table 1. ) Was prepared. The results are shown in Table 1 together with the storage stability evaluation results.

＜実施例５＞

<Example 5>

25 parts of isopropyl alcohol-dispersed colloidal silica having a particle size of 10 nm and a solid content concentration of 20% by weight were added to 100 parts of the composition (A-1) of the present invention having a solid content concentration of 20% by weight obtained in Example 1. A composition (A-5) of the present invention having a solid concentration of 20% by weight was obtained. The storage stability was A.
<Example 6>

To 100 parts of the composition (A-1) of the present invention obtained in Example 1, 5 parts of an isopropyl alcohol solution of di-n-butoxy bis (acetylacetonate) zirconium having a solid concentration of 15% by weight was added. After stirring well, it was applied on a Teflon sheet so that the dry film thickness was 100 μm and cured at 100 ° C. for 1 hour to prepare a cured product. As a result of evaluating the stability of the cured product under sulfur exposure, it was A.
<Example 7>

In the same manner as in Example 6 except that the composition (A-2) of the present invention obtained in Example 2 was used instead of the composition (A-1) of the present invention obtained in Example 1, sulfur was used. As a result of evaluating the stability under exposure, it was A.
<Example 8>

In the same manner as in Example 6 except that the composition (A-3) of the present invention obtained in Example 3 was used instead of the composition (A-1) of the present invention obtained in Example 1, sulfur was used. As a result of evaluating the stability under exposure, it was A.
<Example 9>

In the same manner as in Example 6 except that the composition (A-4) of the present invention obtained in Example 4 was used instead of the composition (A-1) of the present invention obtained in Example 1, sulfur was used. As a result of evaluating the stability under exposure, it was A.
<Example 10>

In the same manner as in Example 6 except that the composition (A-5) of the present invention obtained in Example 5 was used instead of the composition (A-1) of the present invention obtained in Example 1, sulfur was used. As a result of evaluating the stability under exposure, it was A.

<Example 11>

To 100 parts of the composition (A-1) of the present invention obtained in Example 1, 5 parts of an isopropyl alcohol solution of di-n-butoxy bis (acetylacetonate) zirconium having a solid concentration of 15% by weight was added. After stirring well, a commercially available surface-mount LED package (with silver plating) was prepared so that the dry film thickness was 100 μm, and dried at 100 ° C. for 1 hour to prepare a sample for evaluating silver blackening inhibition. The silver blackening inhibiting ability of this sample was A.
<Example 12>

In the same manner as in Example 11 except that the composition (A-2) of the present invention obtained in Example 2 was used instead of the composition (A-1) of the present invention obtained in Example 1, silver was used. It was A as a result of evaluating blackening suppression ability.
<Example 13>

In the same manner as in Example 11 except that the composition (A-3) of the present invention obtained in Example 3 was used instead of the composition (A-1) of the present invention obtained in Example 1, silver was used. It was A as a result of evaluating blackening suppression ability.
<Example 14>

In the same manner as in Example 11 except that the composition (A-4) of the present invention obtained in Example 4 was used instead of the composition (A-1) of the present invention obtained in Example 1, silver was used. It was A as a result of evaluating blackening suppression ability.
<Example 15>

In the same manner as in Example 11 except that the composition (A-5) of the present invention obtained in Example 5 was used instead of the composition (A-1) of the present invention obtained in Example 1, silver was used. It was A as a result of evaluating blackening suppression ability.
[Comparative Example 1]
Mix 60 parts of Daicel Chemical Industries' CE2021 as an alicyclic epoxy resin, 66 parts of Nippon Steel Chemical Co., Ltd. MH700 as an acid anhydride, and 0.7 part of UCAT18X from San Apro as a curing accelerator. After stirring, it was applied on a Teflon sheet so that the dry film thickness was 100 μm, and cured at 100 ° C. for 1 hour to prepare a cured product. As a result of evaluating the stability of the cured product under sulfur exposure, it was C.
[Comparative Example 2]
A commercially available surface-mount LED package (with silver plating) with a silicone encapsulant based on linear polydimethylsiloxane (Momentive Performance Materials TSE3033A, TSE3033B) with a dry film thickness of 100 μm ) And dried at 150 ° C. for 5 hours to prepare a sample for evaluating silver blackening suppression ability. The silver blackening inhibiting ability of this sample was C.

It is a schematic diagram of the light emitting diode using the coating material of this invention. It is a schematic diagram of the light emitting diode using the coating material of this invention. It is a schematic diagram of the light emitting diode using the coating material of this invention containing the fluorescence part.

Explanation of symbols

50 Light-Emitting Element 51 Sealing Material 52 Phosphor 53 Coating Material 55 of the Present Invention Silver Electrode

Claims (8)

Following formula (1)
R ¹ _n Si (OR ² ) _4-n (1)
(Wherein, R ¹ represents a monovalent organic group having 1 to 8 carbon atoms, optionally .R ² be different be the same as each other, if present two are each independently carbon An alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, n is an integer of 0 to 2)
At least one silane compound (a1) selected from the group consisting of at least one organosilane, a hydrolyzate of the organosilane and a condensate of the organosilane, and a hydrolyzable group and / or A metal coating material comprising a polymer (A) obtained by subjecting a polymer (a2) having a silyl group containing a silicon atom bonded to a hydroxyl group to a hydrolysis / condensation reaction.   The content of the silane compound (a1) and the polymer (a2) in terms of the complete hydrolysis condensate of the silane compound (a1) (Wa1) and the content of the polymer (a2) in terms of solid content (Wa2) The weight ratio (Wa1 / Wa2) is in the range of 5/95 to 95/5 [Wa1 + Wa2 = 100. The metal coating material according to claim 1, wherein the metal coating material is hydrolyzed and condensed.   In the polymer (a2), the content of a silyl group containing a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group is 0.1 to 2% by weight in terms of the silicon atom content. The metal coating material according to claim 1 or 2.   (B) The metal coating material according to any one of claims 1 to 3, further comprising silica.   It is used for silver, The metal coating material in any one of Claims 1-4 characterized by the above-mentioned.   It is used for a silver electrode, The metal coating material in any one of Claims 1-5 characterized by the above-mentioned.   A light-emitting device comprising a silver-plated member and / or a silver electrode coated with the metal coating material according to claim 1.   A method for protecting the metal by applying the metal coating material according to claim 1 to a metal surface.

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