JP2002155200A - Weatherproof resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a weatherproof organic silicone resin composition without greatly damaging general properties required for a sealing material, paint, adhesive, casting material, coating material, etc. SOLUTION: This composition comprises 100 parts by mass organic silicone polymer (1) with a polyoxyalkylene main chain and a reactive silicon group, -SiXaR3-a wherein R is a substituted or non-substituted monovalent organic group, X is an OH group or a hydrolyzable group, and a is a number of 1, 2, or 3, at the end of the molecule, and 0.1-100 parts by mass compound (2) obtainable by reacting a silicon compound having an organic group having an NCO group in the group, and an alkoxyl group or an acetoxyl group is bonded to the silicon atom, with a deterioration inhibitor having an NH, OH, COOH, or SH group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a weatherable resin composition, and more particularly, to a sealing material, a paint, an adhesive,
The present invention relates to an organosilicone-based resin composition having excellent weather resistance suitable for applications such as casting materials and coating materials.

[0002]

2. Description of the Related Art Organic silicone resins are widely used in applications such as sealing materials, paints, adhesives, casting materials and coating materials. In these applications, there is a problem that the surface is exposed to outside air and deteriorates. In order to impart the weather resistance of the organic silicone resin, it is common practice to mix various antioxidants, ultraviolet absorbers, light stabilizers and other antioxidants, but these antioxidants are hydrophilic. Since it has a functional group, it gradually flows out by rainwater or the like, and the effect of preventing deterioration due to the addition of the deterioration preventing agent cannot be maintained for a long time.

[0003]

SUMMARY OF THE INVENTION The present invention relates to an organosilicone resin composition having excellent weather resistance without greatly impairing general performance required for sealing materials, paints, adhesives, casting materials, coating materials, and the like. The purpose is to provide things.

[0004]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies. As a result, rather than simply blending the above-mentioned deterioration inhibitor into an organic silicone resin,
The object of the present invention is to provide a resin composition obtained by blending a reaction product of a silicon compound having a hydrolyzable group possessed by a conventional organic silicone-based resin with the above-mentioned deterioration inhibitor into an organic silicone-based resin. It has been found that the present invention can be achieved, and arrived at the present invention.

That is, the present invention relates to (1) a polyoxyalkylene having a main chain having a reactive silicon group at the molecular terminal.
—SiX _a R _3-a (R is a substituted or unsubstituted monovalent organic group having 1 to 10 carbon atoms, X is a hydroxy group or a hydrolyzable group, and a is 1, 2 or 3). (2) A silicon compound having an organic group (I) having an isocyanate group in its group and a hydrolyzable group selected from an alkoxy group and an acetoxy group directly bonded to a silicon atom Compound (Synthesis A) obtained by reacting (compound (a)) with a deterioration inhibitor (compound (b)) having a secondary amino group, a hydroxy group, a carboxy group, a mercapto group and / or a primary amino group ) The gist of the present invention is a weatherable resin composition containing 0.1 to 100 parts by mass as a component (hereinafter, referred to as composition 1).

The composition 1 of the present invention is characterized in that the compound (a) has an organic group having at least one group selected from a primary amino group, a secondary amino group and a (meth) acryloyl group. One or more compounds (compounds (c)) having a hydrolyzable group selected from an alkoxy group and an acetoxy group directly bonded to 1 to 10 silicon atoms, and an organic group Less than two activities belonging to a secondary amino group in one molecule obtained by reacting with an organic compound (compound (d)) capable of producing a compound having a secondary amino group by reacting with (II) Compound having hydrogen and the hydrolyzable group directly bonded to 1 to 10 silicon atoms (synthetic compound B)
Or an organic group (III) having one mercapto group or a secondary amino group in the group, and a hydrolyzable group selected from an alkoxy group and an acetoxy group is directly bonded to 1 to 3 silicon atoms. It is a compound (synthetic product C) obtained by reacting a silicon compound (compound (e)) with a compound having two or more isocyanate groups in its molecule (compound (f)).

The composition 1 of the present invention is a compound (compound (c-1)) in which the compound (c) is a group in which the organic group (II) has one primary amino group. The compound (d) is an α, β-unsaturated carbonyl compound (compound (g)), an α, β-unsaturated nitrile compound (compound (h)) and / or a carbonate compound (compound (i)). It is characterized by. The composition 1 of the present invention is characterized in that the compound (c) is a compound in which the organic group (II) is a group having two or more primary amino groups or secondary amino groups, or a primary amino group and a secondary amino group. A compound having one or more (compound (c-2)), wherein the compound (d) is the compound (g), the compound (h),
Reaction of the above compound (i) with a compound having two or more isocyanate groups (compound (j)) and a compound having one or two active hydrogens capable of reacting with an isocyanate group in the molecule (compound (k)) It is characterized by being a compound (compound (l)) and / or a monoisocyanate compound (compound (m)) having less than two isocyanate groups in its molecule. The composition 1 of the present invention is characterized in that the compound (k) is a compound selected from a monoalcohol, a monoprimary amine, a monosecondary amine, a monocarboxylic acid, and a monothiol. Further, the composition 1 of the present invention is characterized in that the compound (c) is a compound (compound (c-) in which the organic group (II) has a (meth) acryloyl group.
3)), wherein the compound (d) is a mono-primary amine compound (compound (n)), or two or more primary amino groups or secondary amino groups, or one or more primary amino groups and secondary amino groups Reaction product of a compound having the formula (compound (o)) with the compound (g), the compound (h), the compound (i), the compound (l), or the compound (m) (compound (p)) It is characterized by being.

Further, the present invention relates to (1) a method wherein (1) the main chain is polyoxyalkylene, and a reactive silicon group -S
iX _a R _3-a (R is a substituted or unsubstituted monovalent organic group having 1 to 10 carbon atoms, X is a hydroxy group or a hydrolyzable group, and a is 1, 2 or 3). 100 parts by mass of an organic silicone polymer and (2) an organic group (IV) having a (meth) acryloyl group in the group, and a hydrolyzable group selected from an alkoxy group and an acetoxy group was directly bonded to a silicon atom. Compound (synthesis D) 0.1 obtained by reacting a compound (compound (q)) with a deterioration inhibitor (compound (r)) having a secondary amino group, a mercapto group and / or a primary amino group (compound D) -30 parts by mass of a weather-resistant resin composition (hereinafter, referred to as composition 2).
Is the gist.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The organosilicone polymer which is one component of the weatherable resin composition of the present invention has a polyoxyalkylene main chain and a reactive silicon group -Si
X _a R _3-a (R is a substituted or unsubstituted monovalent organic group having 1 to 10 carbon atoms, X is a hydroxy group or a hydrolyzable group, and a is 1, 2 or 3). It can be widely used.

R of the reactive silicon group is a substituted or unsubstituted monovalent organic group having 1 to 10 carbon atoms, preferably an alkyl group having 8 or less carbon atoms, a cycloalkyl group, a phenyl group or a fluoroalkyl group. Groups, particularly preferably methyl, ethyl, propyl, butyl, hexyl, octyl,
And cyclohexyl and phenyl groups. When there are a plurality of Rs, those Rs may be the same or different.
Examples of the hydrolyzable group for X include a halogen atom, an alkoxy group, an acyloxy group, an amide group, an amino group, an aminooxy group, a ketoximate group, a hydride group and the like. Among these, the number of hydrolyzable carbon atoms having a carbon atom is preferably 6 or less, and particularly preferably 4 or less. Preferred X is a lower alkoxy group having 4 or less carbon atoms, particularly a methoxy group, an ethoxy group, a propoxy group,
An example is a propenyloxy group. When there are a plurality of Xs, those Xs may be the same or different.

As described above, any of such organic silicone polymers can be used as long as the main chain is a polyoxyalkylene and the terminal has the above-mentioned reactive silicon group. They are already widely used, and typically, (1) those commonly referred to as modified silicone resins, and (2) those having a urethane bond therein.

As a method for producing the above (1),
Polyoxyalkylene polymerization having functional groups such as roxy groups
With the above-mentioned reactivity via any organic group at the terminal
A method of producing by introducing a silicon group is typical. Raw material po
Introducing the above reactive silicon group into the lioxyalkylene polymer
Examples of the method include the following methods (I) to (IV).
It is. (I) Powder of polyoxyalkylene polymer having hydroxyl group
After introducing an olefin group at the end, the formula HSix_aR_3-a
Reacting a hydrosilyl compound represented by the formula (Formula
Wherein R, X and a are as defined above. (II) Powder of polyoxyalkylene polymer having hydroxyl group
At the end, the formula R_3-aSix _aR^TwoIsoshi represented by NCO
A method of reacting an anatsilyl compound (where R, X
And a are as defined above, R^TwoIs divalent having 1 to 17 carbon atoms
Is a hydrocarbon group). (III) Polyoxyalkylene polymer having hydroxyl group
At the end, a polyisocyanate such as tolylene diisocyanate
After reacting the compound to make the isocyanate group terminal,
Formula R_3-aSix_aR^TwoReacts silicon compound represented by W
Wherein R, X and a are as defined above, and W is
Hydroxyl, carboxy, mercapto and amino groups (1
Active hydrogen group selected from primary or secondary)). (IV) Powder of polyoxyalkylene polymer having hydroxyl group
After introducing an olefin group at the end, the olefin group and W
Is a mercapto group.
A method of reacting a rucapto group.

Typical examples of the method for producing the organosilicone polymer of the above (1) include, for example, JP-A-50-156599, JP-A-54-6096 and JP-A-55-6096.
Nos. 82123, 55-13022 and 55-13
No. 7129, No. 57-126823, No. 59-782
No. 23, No. 59-168014, No. 60-22851
No. 7, No. 60-228516, No. 61-34067
No. 62-280217, No. 62-230822
Nos. 63-6041, 63-11624 and 6
JP-A-3-254129 and JP-A-63-83131;
-131271, 1-236258, 1-27
No. 5648, No. 2-214759, No. 1-2904
Nos. 1-338407, 3-47825, 3-
No. 72527, No. 3-122152, No. 5-8632
No. 5, 6-172631, 8-12723, 10-251552, 10-251272, 1
No. 0-204144, No. 10-195151, No. 11
-116831, 11-124509, WO
98/47939, WO 97/06194, U.S. Pat. Nos. 3,632,557 and 4,345,053.
And Nos. 4,366,307 and 4,960,844.

The method for producing the above (2) is as follows.
A typical method is to provide a urethane bond to the polyoxyalkylene polymer and introduce the reactive silicon group to produce the polyoxyalkylene polymer. Examples of the method for producing the organosilicone polymer of the above (2) include, for example, JP-A-8-283366, JP-A-2000-143775, and WO98 / 5800.
No. 5, JP Patent No. 3030020, JP Patent No. 25940
No. 24 and the like.

The organic silicone polymer is called a modified silicone resin and has a number average molecular weight of 500 to 50,0.
A wide range of 00 is commercially available, and they can be suitably used.

The composition 1 of the present invention contains an organosilicone polymer and the above-mentioned compound A as active ingredients. Can be synthesized. The compound (a) is a known compound, and a commercially available product can be used. And the compound C obtained by reacting the compound (f) with the compound (f).

In the following, each compound used for producing Compound B and Compound C will be described.

As the compound (c), compounds having an organic group (II) having less than two secondary amino groups only are excluded, and γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ -Aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, δ-aminobutyltriethoxysilane,
γ- (m-aminophenoxy) propyltrimethoxysilane, m-aminophenyltrimethoxysilane, p-aminophenyltrimethoxysilane, (m) (p) -aminophenyltrimethoxysilane, γ- (γ-aminopropoxy) The above organic group (II) such as -γ, γ-dimethyl-α-propenyltrimethoxysilane, γ-aminopropyldiisopropylethoxysilane, γ-aminopropylmethylbis (trimethylsiloxy) silane, γ-aminopropyldimethylethoxysilane; Compound (c-1) which is a group having one primary amino group, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β
(Aminoethyl) -γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ-
Aminoisobutylmethyldimethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N
-(6-aminohexyl) aminopropyltrimethoxysilane, ureapropyltriethoxysilane, ureapropyltrimethoxysilane, and other specialty aminosilanes manufactured by Shin-Etsu Chemical Co., Ltd., trade names: KBM6063, X-12
-896, KBM576, X-12-565, X-12
-580, X-12-806, X-12-666, X-
12-5263, KBM6123, X-12-577,
X-12-575, X-12-563B, X-12-5
A compound wherein the organic group (II) such as 62 is a group having two or more primary amino groups or secondary amino groups or a compound (c-2) which is a group having one or more primary amino group and one or more secondary amino group Such as (c-3), wherein the organic group (II) is a group having a (meth) acryloyl group, such as γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, etc. But are not limited to these. When the composition of the present invention is used as a sealing agent, the compound (c) is preferably a compound having an alkyldialkoxysilyl group, particularly a methyldimethoxysilyl group, among the above compounds.

The compound (d) includes an α, β-unsaturated carboxy compound, an α, β-unsaturated ketone compound,
α, β-unsaturated carbonyl compounds such as α, β-unsaturated aldehyde compounds (compound (g)), α, β-unsaturated nitrile compounds (compound (h)) (compounds (g) and (h) ) Contains no hydroxy group), a carbonate compound (compound (i)), a compound having two or more isocyanate groups (compound (j)) and one or two active hydrogens capable of reacting with an isocyanate group in the molecule. A compound having less than 2 isocyanate groups in its molecule (compound (l)) obtained by reacting the compound (compound (k))
Monoisocyanate compound (compound (m)), monoprimary amine (compound (n)) or a compound having two or more primary or secondary amino groups or one or more primary and secondary amino groups (compound (O)) and a reaction product (compound (p)) of the compound (g), the compound (h), the compound (i), the compound (l), or the compound (m).

As the compound (g), methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, 2-methoxyethyl (meth)
Acrylate, cyclohexyl (meth) acrylate,
Benzyl (meth) acrylate, isobornyl (meth)
Acrylate, dicyclopentadienyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, n-stearyl (meth) acrylate, dodecyl (meth) acrylate, 2-cyanoacrylate, 2- Acrylic esters such as ethyl cyanoacrylate, monofunctional special acrylates manufactured by Toagosei Co., Ltd. (trade name: ARONIX M-10)
1, M-102, M-110, M-111, M-11
3, M-117, M-120, M-156, M-530
0, M-5400, M-5600, M-5700, etc.),
Product name: Daicel Chemical Industries, Ltd .: Plaxel FA-1
(Meth) acryloxysilanes such as γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, N-cyclohexylmaleimide, N-phenylmaleimide, N-
Monomaleimides such as lauryl maleimide and diethyl phenyl maleimide; maleic anhydrides such as maleic anhydride, dimethyl maleate, diethyl maleate, dibutyl maleate and di-n-butyl maleate; and fumaric esters such as diethyl fumarate. Can be Examples of the compound (h) include acrylonitrile.

The carbonate compound of the compound (i) is an organic carbonate compound, and examples thereof include cyclic carbonate compounds such as propylene carbonate, ethylene carbonate, norbornane cyclic carbonate and norbornene cyclic carbonate, and dimethyl carbonate and diphenyl carbonate. Carbonate compounds are preferred, and propylene carbonate and ethylene carbonate are particularly preferred. As the norbornane cyclic carbonate and norbornene cyclic carbonate, those produced by a known method, for example, a method described in the 39th Annual Meeting of the Society of Polymer Science, 284 (1990) can be used. More specifically, an aqueous solution of potassium hydroxide or the like is added dropwise to a mixture of norbornene aldehyde, an aqueous formaldehyde solution and methanol to form norbornene-
5,5-dimethanol is obtained. Norbornene-5,5-
Hydrogen reduction of dimethanol in the presence of palladium carbon gives norbornane-5,5-dimethanol. When a mixture of norbornene-5,5-dimethanol or norbornane-5,5-dimethanol and ethyl chloroformate is dropped and reacted with triethylamine or the like, norbornene cyclic carbonate or norbornane cyclic carbonate can be produced. it can.

The compound (j) includes a diisocyanate compound and a polyisocyanate compound excluding the diisocyanate compound. Examples of the diisocyanate compound include aliphatic, alicyclic, araliphatic, and aromatic diisocyanate compounds. Hereinafter, specific examples thereof will be described.

Aliphatic diisocyanate compounds: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene Diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate and the like. Alicyclic diisocyanate compound: 1,3-cyclopentene diisocyanate, 1,4
-Cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-
3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and the like. Aromatic diisocyanate compound: 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω,
ω'-diisocyanate-1,4-diethylbenzene,
1,3- or 1,4-bis (1-isocyanate-
1-methylethyl) benzene or a mixture thereof. Aromatic diisocyanate compound: m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4 '
-Diphenyl diisocyanate, 1,5-naphthalenediisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 4,
4'-diphenyl ether diisocyanate and the like.

Examples of the polyisocyanate compound other than the diisocyanate compound include aliphatic, alicyclic, araliphatic, and aromatic polyisocyanate compounds. Hereinafter, specific examples thereof will be described.

Aliphatic polyisocyanate compounds: lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,3 6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanatomethyloctane and the like. Alicyclic polyisocyanate compound: 1,3,5-triisocyanatecyclohexane, 1,3,5-trimethylisocyanatecyclohexane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexylisocyanate, 2- (3-isocyanatepropyl) −2,5-
Di (isocyanatomethyl) -bicyclo [2,2,1]
Heptane, 2- (3-isocyanatopropyl) -2,
6-di (isocyanatomethyl) -bicyclo [2,2,
1] heptane, 3- (3-isocyanatopropyl)-
2,5-di (isocyanatomethyl) -bicyclo [2,
2,1] heptane, 5- (2-isocyanatoethyl)
-2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane, 6-
(2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3- Isocyanatopropyl) -bicyclo [2,2,1] heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl)-
Bicyclo [2,2,1] heptane and the like. Aromatic polyisocyanate compound: 1,3,5-triisocyanatomethylbenzene and the like. Aromatic polyisocyanate compound:
Triphenylmethane-4,4 ', 4 "-triisocyanate, 1,3,5-triisocyanatebenzene, 2,
4,6-triisocyanate toluene, 4,4'-diphenylmethane-2,2 ', 5,5'-tetraisocyanate and the like.

Examples of the compound (k) include monoalcohols, monoprimary amines, monosecondary amines, monocarboxylic acids, monothiols, and carbonate compounds. As the monoalcohol, among the compounds represented by the general formula of ROH, a primary amino group, a secondary amino group,
This is a monoalcohol having no group that reacts with an isocyanate group other than a hydroxy group, such as a carboxyl group or a mercapto group. Monomers of diols such as ethylene glycol monobutyl ether and propylene glycol monobutyl ether, monoesters of polyester diols such as diethylene glycol monobutyl ester, and aromatic compounds such as phenol are also included. Further, a tackifying compound of a terpene phenol having a hydroxy group is also included.

As the mono-primary amine, among the compounds represented by the general formula of RNH _2, a group which reacts with an isocyanate group other than a primary amino group, such as a hydroxy group, a secondary amino group, a carboxy group or a mercapto group. It is a mono-primary amine that does not have. Also included are aminosilanes such as γ-aminopropyltrimethoxysilane and aromatic compounds such as aniline and benzylamine. As the monosecondary amine, among the compounds represented by the general formula of RNHR ', there is no group that reacts with an isocyanate group other than the secondary amino group, such as a hydroxy group, a primary amino group, a carboxy group or a mercapto group. It is a mono-secondary amine. Also included are arylaminosilanes such as N-phenyl-γ-aminopropyltrimethoxysilane and heterocyclic compounds such as pyridine and piperidine. Further, as the mono-primary amine and the mono-secondary amine, tackifying compounds such as aminosilane and rosin having an amino group are also included.

As the carboxylic acid, among the compounds represented by the general formula of RCOOH, those which do not have a group which does not react with an isocyanate group other than a carboxy group, such as a hydroxy group, a primary amino group, a secondary amino group or a mercapto group. It is a carboxylic acid compound. Aromatic compounds such as benzoic acid are also included. Further, a tackifier such as a rosin ester having a carboxy group is also included. As monothiol,
Among the compounds represented by the general formula of RSH, it is a monothiol having no group that reacts with an isocyanate group other than a mercapto group, such as a hydroxy group, a primary amino group, a secondary amino group, or a carboxy group. γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane and the like are also included. Further, the carbonate compound can be selected from the above compounds (i).

The compound (l) can be produced by reacting the compound (j) with the compound (k). In the reaction between compound (j) and compound (k), assuming that the number of organic groups (II) in compound (c) is α, 1 mol of compound (j) and compound (k) (α-1) × (0.1 ~
1.9) moles at temperatures of -20 to + 150 ° C., from 1 to 1,
It is performed for about 000 hours.

Examples of the monoisocyanate as the compound (m) include R such as ethyl isocyanate, n-dodecyl isocyanate, p-toluenesulfonyl isocyanate, n-hexyl isocyanate, benzyl isocyanate and 2-methoxyphenyl isocyanate. -In addition to the compound represented by the general formula of NCO, a product name: KBE9 manufactured by Shin-Etsu Chemical Co., Ltd.
007 and the like.

As the compound (n), propylamine,
Butylamine, isobutylamine, 2-butylamine,
1,2-dimethylpropylamine, hexylamine, 2
-Ethylhexylamine, amylamine, 3-pentylamine, isoamylamine, 2-octylamine, 3-
Examples include methoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, rosinamine and the like. These can be used alone or in combination of two or more.

As the compound (o), N-methyl-3,
3'-iminobis (propylamine), ethylenediamine
Diethylene triamine, triethylene diamine,
Ethylenediamine, 1,2-diaminopropane,
1,3-diaminopropane, 1,2-diaminobutane,
1,4-diaminobutane, 1,9-diaminononane, A
TU (3,9-bis (3-aminopropyl) -2,4
8,10-tetraoxaspiro [5.5] undeca
), CTU guanamine, dodecanoic dihydrazide, f
Xamethylenediamine, m-xylylenediamine, dia
Nisidine, 4,4'-diamino-3,3'-diethyldi
Phenylmethane, diaminodiphenyl ether, 3,
3'-dimethyl-4,4'-diaminodiphenyl meta
, Tolidine base, m-toluylenediamine, o-olefin
Phenylene diamine, m-phenylene diamine, p-phenylene
Nilendiamine, melamine, 1,3-diphenylguani
Gin, di-o-tolylguanidine, bis (aminopropyl
Ru) piperazine, N- (3-aminopropyl) -1,3
-Propanediamine, bis (3-aminopropyl) A
Compounds having multiple primary amino groups such as ter, pipera
Gin, cis-2,6-dimethylpiperazine, cis-2,
5-dimethylpiperazine, 2-methylpiperazine, N,
N'-di-t-butylethylenediamine, 2-aminomethyl
Tilpiperidine, 4-aminomethylpiperidine, 1,3
-Di- (4-piperidyl) -propane, 4-aminopro
Pyraniline, homopiperazine, N, N'-diphenyl
Thiourea, N, N'-diethylthiourea, N-methyl-
A plurality of secondary amino groups such as 1,3-propanediamine
Compounds, furthermore, methylaminopropylamine, d.
Tylaminopropylamine, ethylaminoethylamido
, Laurylaminopropylamine, 2-hydroxyd
Tylaminopropylamine, 1- (2-aminoethyl)
Piperazine, N-aminopropylpiperazine, 3-amido
Nopyrrolidine, N-phenyl-γ-aminopropyltri
Methoxysilane, 1-o-tolylbiguanide, 2-amido
Nomethylpiperazine, N-aminopropylaniline,
Tylamine ethylamine, 2-hydroxyethylamino
Propylamine, laurylaminopropylamine, 2-
Aminomethylpiperidine, 4-aminomethylpiperidi
H_TwoN (C _TwoH_FourNH)_nH (n ≧ 5)
(Polyate, manufactured by Tosoh Corporation)
I can do it. These can be used alone or in combination of two or more.

The compound (p) is obtained by reacting the compound (o) with the compound (g), the compound (h), the compound (i), the compound (l) or the compound (m). There is something. The reaction of the compound (o) with the compound (g), the compound (h), the compound (i), the compound (l) or the compound (m) is carried out by determining the number of active hydrogens in the compound (o) by β
Where 1 mol of compound (o) and compound (g), compound (h), compound (i), compound (l) or compound (m) (β-1) × (0.1 to 1.9) The mole is -20
This is performed at a temperature of + 150 ° C. for about 1 to 1,000 hours.

As the compound (e), the compound (c-
In addition to selecting a compound having a secondary amino group from 2), N- (n-butyl) aminopropyltrimethoxysilane, N-phenyl-α-aminopropyltrimethoxysilane, and further γ-mercaptopropyltrimethoxysilane Methoxysilane, γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltriethoxysilane, γ-
Compounds having a mercapto group such as mercaptopropyldiethoxymethylsilane are exemplified.

Compound (f) used in producing Compound C by reacting with Compound B or Compound (e).
Can be selected from the above compounds (j), but those having a molecular weight of 1,000 or less are desirable.

The compound (a) used in the present invention is
Preferably, the compound B or the compound (e) obtained by reacting the compound (c) with the compound (d),
Compound C obtained by reacting the compound (f). The compound (c) and the compound (d) are at -20 ° C
Reaction at a temperature of about 150 ° C. for 1 to 1,000 hours,
2 belonging to a secondary amino group (-NH-) in one molecule
A compound A having less than one, preferably 0.1 to 1.5 active hydrogens and having 1 to 10 hydrolyzable groups directly bonded to a silicon atom is synthesized. The reaction may be performed in the presence of a medium such as an organic solvent, and there is no problem if the reaction is performed for more than 1,000 hours. Compound (c) and compound (d) are
Not only one type but also two or more types may be used. The ratio of the compound (c) to the compound (d) used is usually 1 mol of the compound (c), and the compound (d) is usually composed of the organic group (II) in the compound (c).
Is about (γ-1) × (0.1 to 9) mol, but is appropriately adjusted according to the reaction conditions, the odor generated, and the like.

The compound B and the compound (f) are represented by
The reaction is carried out at a temperature of about 20 ° C. to 150 ° C. for 1 to 1,000 hours, and less than two, preferably 0.1 to
The above-mentioned compound B having 1.5 isocyanate groups is synthesized. The reaction may be performed in the presence of a medium such as an organic solvent, and there is no problem if the reaction is performed for more than 1,000 hours.
The compound (f) is not limited to one type, and two or more types may be used. The ratio of the compound B and the compound (f) used is as follows, where δ is the number of active hydrogens belonging to the secondary amino group of the compound B.
The compound (f) is used in a range of about (δ-1) × (0.1 to 9) mol. The compound (e) and the compound (f) are reacted in the same manner as the compound B and the compound (f) to synthesize the compound C. The compound (e) and the compound (f) are not limited to one type, and two or more types may be used.
When the number of organic groups (III) in the compound (e) is represented by ε, the compound (e) and the compound (f) are usually expressed as (ε -1) × (0.1 to
9) It is used in a range of about mol.

Compound A, which is one component of the composition 1 of the present invention
As the compound (a) used for producing
The synthesized product C produced as described above is preferable, but a commercially available product can also be used. Such commercial products include:
γ-isocyanatopropyltriethoxysilane, γ-
Isocyanatepropyltrimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and the like.

Compound A which is a component of the composition 1 of the present invention
Is used in the production of the compound (a), and a deterioration inhibitor (compound (b)) which reacts with the compound (a) has a secondary amino group, a hydroxy group, a carboxy group, a mercapto group and / or a primary amino group in its molecule. And compounds other than compounds having a primary amino group in the molecule are widely used as deterioration inhibitors for various resins.

Examples of compounds other than those having a primary amino group include poly [(6-morpholino-s-triazine-2,4-diyl)} 2 as a compound having a secondary amino group in the molecule. , 2,6,6-tetramethyl-4-piperidyl) imino {hexamethylene} 2
2,6,6-tetramethyl-4-piperidyl) imino}], bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl- 4-piperidyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, poly (2,2,4-trimethyl-1,2-dihydroquinoline), 6-ethoxy-2,2, 4-trimethyl-1,2-dihydroquinoline, N, N'-diphenyl-p-phenylenediamine, N-isopropyl-N'-
Phenyl-p-phenylenediamine, N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine, mixed N, N'-diallyl-p-phenylenediamine, alkylated diphenylamine, 8-acetyl-3-
Dodecyl-7,7,9,9-tetramethyl-1,3,8
-Triazaspiro [4.5] decane-2,4-dione,
Poly [｛6- (1,1,3,3-tetramethylbutyl)
Amino-1,3,5-triazine-2,4-diyl
{2,2,6,6-tetramethyl-4-piperidyl) imino {hexamethylene {2,2,6,6-tetramethyl-4-piperidyl) imino}], N, N'-bis (3-
Aminopropyl) ethylenediamine-2, -bis [N-
Butyl-N- (1,2,2,6,6-pentamethyl-4
-Piperidyl) amino] -6-chloro-1,3,5-triazine condensate, diphenylguanidine, di-o-tolylguanidine, N-cyclohexylbenzothiazyl-sulfenamide and the like.

Compounds having a hydroxy group in the molecule include 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy -4-methoxybenzophenone trihydrate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfate trihydrate, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2 -Hydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-oct Xybenzophenone, 2- ( '- hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2
-(2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'
-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) -5
-Chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-t-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole, 2- (2 -Hydroxy-5-methylphenyl) -2H-benzotriazole, 5-chloro-2- (3,5-di-t-butyl-2-)
(Hydroxyphenyl) -2H-benzotriazole, 2
-(3-t-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole, 2-
(3,5-di-t-pentyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-
t-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-t-octylphenyl) -2H-benzotriazole, 2- [2 '
-Hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimido-methyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-amylphenyl) benzotriazole, 2- (2-hydroxy-3-dodecyl-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, n-hexadecyl-
3,5-di-t-butyl-4-hydroxybenzoate, n-hexadecyl-3,5-di-t-butyl-4-
Hydroxybenzoate, 2 ', 4'-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 1,3,5-tris (4-tert-butyl-3
-Hydroxy-2,6-dimethylbenzyl) isocyanuric acid, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-t-butyl) -4-hydroxybenzyl)
Isocyanuric acid, ethylene glycol bis [3- (3-
t-butyl-4-hydroxy-5-methylphenyl) propionate], tetrakis [methylene-3 (3 ',
5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, n-octadecyl-3 (3 ',
5'-di-t-butyl-4'-hydroxyphenyl) propionate, triethylene glycol bis [3-
(3-t-butyl-4-hydroxy-5-methylphenyl) propionate], isooctyl-3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol bis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,
5-di-t-butyl-4-hydroxyphenyl) propionate], 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), 2,2'-butylidene-bis (4-methyl-6 -T-butylphenol),
2,2'-butylidene-bis (4-ethyl-6-t-butylphenol), 4,4'-thio-bis (3-methyl-6-t-butylphenol), 2,2'-methylene-
Bis [4-methyl-6-t-butylphenol], 2,
2'-methylene-bis (4-methyl-t-butylphenol), 2,2'-methylene-bis (4-ethyl-t-
Butylphenol), 6- (2-benzotriazolyl)
-4-tert-octyl-6'-tert-butyl-4'-methyl-2,2'-methylenebisphenol, styrenated phenol, 2,6-di-tert-butyl-4-methylphenol, 2,4- Dimethyl-6- (1-methylcyclohexyl) phenol, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl]-
5- (octyloxy) phenol, 2,6-di-t-
Butyl-4-ethylphenol, 2- (2H-benzotriazol-2-yl) -4-menthyl-6- (3,
4,5,6-tetrahydrophthalimidylmethyl) phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol, 2,5- Di-t-butylhydroquinone, poly (2,2,4-trimethyl-1,2-dihydroquinone), 6-ethoxy-2,2,4-trimethyl-1,2
-Dihydroquinone, 2,5-di-t-amylhydroquinone, 4,4'-butylidene-bis (6-t-butyl-m-cresol), 2,2'-methylene-bis [6-
(1-methylcyclohexyl) -p-cresol], 1
-[2- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4-
{3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-tetramethylpiperidine, S- (3,5-di-t-butyl-4)
-Hydroxybenzyl) -2-ethyl-n-hexyl-
Thioglycolate, 4,4'-thiobis (6-t-butyl-m-cresol), p-benzoquinonedioxime,
1,6-bis (4-benzoyl-3-hydroxyphenoxy) -hexane, 1,4-bis (4-benzoyl-3)
-Hydroxyphenoxy) -butane, phenyl salicylate, 4-t-butylphenyl salicylate, 1,1,3
-Tris (2-methyl-t-butyl-4-hydroxy-
5-t-butylphenyl) butane, 1,1-bis (4-
Hydroxyphenyl) cyclohexane, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-
Methylphenyl) propionyloxy {-1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2-t-butyl-6- (3'-
t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine Polycondensates,
A condensate of methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol,
3,4-dihydro-2,5,7,8-tetramethyl-2
-(4,8,12-trimethyltridecyl) -2H-benzopyran-6-ol (Irganox E20
1), a mixture of Irganox E201, glycerin and low-density polyethylene, a mixture of Irganox E201 and stearic acid, calcium bis (3,5-di-t-butyl-4-hydroxybenzylsulfonate) calcium and polyethylene wax A mixture with 2,4-bis [(octylthio) methyl] -o-cresol, N,
N'-hexamethylenebis (3,5-di-t-butyl-
4-hydroxy-hydrocinnamide), 3,5-di-t
-Butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-
Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and the like.

Compounds having a secondary amino group and a hydroxy group in the molecule include bis (1,2,3-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate. , 2,6,6-pentamethyl-4-piperidyl), 2 ', 3-bis [{3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl}] propionohydrazide, 2,4 -Bis (n-octylthio)
-6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine and the like.

Examples of the compound having a hydroxy group and a carboxy group in the molecule include 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

The compound having a mercapto group in the molecule is, for example, mercaptobenzothiazole, and the compound having a secondary amino group and a mercapto group in the molecule is, for example, 2
-Mercaptobenzimidazole and the like.

The compound having a primary amino group in the molecule includes the compound (j) (compound having two or more isocyanate groups) in addition to the compound having a secondary amino group and / or a hydroxy group in the molecule. ) And further reacting a compound having two or more primary amino groups. As the compound (j),
It can be selected from the compounds exemplified above.
Examples of the compound having two or more primary amino groups include hexamethylenediamine, diethylenetriamine, and ethylenediamine.

The method of producing the compound A by reacting the compound (a) with the compound (b) is as follows. The compound (a) is preferably 0.2 equivalent to the active hydrogen of the compound (b). As described above, the reaction is more preferably carried out at a ratio within a range of 1 to 10 equivalents. The reaction between the compound (a) and the compound (b) is preferably performed in an atmosphere of an inert gas such as nitrogen gas at a temperature of room temperature to 200 ° C. and 1 to 1,000.
It is desirable to do it for hours. This reaction can also be carried out in the presence of a medium such as an organic solvent.

The composition 1 of the present invention comprises 100 parts by mass of the organic silicone polymer and 0.1 to 100 parts by mass, preferably 0.5 to 10 parts by mass of the synthetic product A.

The present invention also relates to a weather-resistant resin composition (composition comprising 100 parts by mass of the above-mentioned organosilicone polymer and 0.1 to 30 parts by mass, preferably 0.5 to 5 parts by mass of the above-mentioned compound D). 2) is the gist. Synthetic product D can be produced by reacting compound (q) with compound (r). As the compound (q), in addition to being able to be selected from the compound (c-3) having a (meth) acryloyl group in the compound (c),
It can be produced by reacting the compound B or the compound (e) with a poly (meth) acrylate.

As the poly (meth) acrylate, for example, Kyoeisha Chemical Co., Ltd., product name: epoxy ester 40E
M, 70PA, 200PA, 80MFA, 3002M,
3002A, 1600A, 3000A, 200EA, 4
00EA, manufactured by Nagase Kasei Kogyo Co., Ltd., trade name: DM-20
1, DM-811, DM-832, DM-851, DA
-722, DA-911, DA-920, DA-93
1, DA-111, DA-141, DA-212, DA
-250, DA-314, DA-721 (above: epoxidized poly (meth) acrylate), manufactured by Kyoeisha Chemical Co., Ltd., trade names: light acrylate HPP-A, PTMGA-2
50, TMP-3EO-A, TMP-A, TMP-6E
O-3A, PE-3A, PE-4A, DPE-6A, B
A-134, G-201P, 3EG-A, 4EG-A,
9EG-A, 14EG-A, NP-A, 1.6HX-
A, 1.9 ND-A, DCP-A, BP-4EA, BP
-4PA; light ester 1.3BG, 1 / 10DC,
3EG, 4EG, 9EG, 14EG, NP, EG, 2E
G, 1.4BG, 1.6HX, 1.9ND, TMP, G
-101P, BP-2EM, P-2M, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester 23G, NPG, 701, B
PE-100, BPE-200, BPE-500, BP
E-1300, A-NPG, APG-200, APG-
400, APG-700, A-BPE-4, 701A
(The above: polyol poly (meth) acrylate), manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester TMPT, A-TM
PT, A-TMM-3, A-TMM-3L, A-TMM
T (above: tri or tetra acrylate), manufactured by NOF Corporation, trade name: Blemmer ADP, PDT-800,
PDET, ADET, PDPT, ADPT, PDC, A
DC, ADBE, PDBP, ADBP, PDBEP, A
DBEP, PDBPT, ADBPT, 43PDBPE-
800B (above: polyol poly (meth) acrylate), manufactured by NOF Corporation, trade name: Blemmer GMR, GM
RR, GAM, GAM-R, GDM (above: glycerol (meth) acrylate), isocyanuric acid EO modified triacrylate, isocyanuric acid EO modified diacrylate, bisphenol F EO modified diacrylate, bisphenol A EO modified diacrylate , Ditrimethylolpropane tetraacrylate, manufactured by Toagosei Co., Ltd., trade names: M-1100, M-1200, M-121
0, M-1310, M-1600 (above: urethane diacrylate), manufactured by Toagosei Co., Ltd., trade name: M-1960
(Above: urethane polyacrylate), tripropylene glycol diacrylate, polybutylene glycol dimethacrylate, pentaerythritol diacrylate, zinc diacrylate and the like.

The compound (r) can be selected from compounds having a secondary amino group and / or a mercapto group in the compound (b). Among the compounds (r), the compound having a primary amino group in the molecule can be produced in the same manner as the compound (b) having a primary amino group in the molecule. The compound (q) is reacted with the compound (r) to produce a synthetic D
The method may be in accordance with the method of producing compound A by reacting compound (a) with compound (b).

The composition 1 of the present invention contains the above-mentioned organosilicone polymer and the above-mentioned compound A, and the composition 2 contains the above-mentioned organosilicone polymer and the above-mentioned compound D, respectively. Adhesives, casting materials, coating materials and the like can be used, furthermore, each composition, in addition to their respective components, the curing catalyst of the organic silicone polymer, tackifying resin, anti-sagging agent, epoxy resin, oligomer, Process oils, fillers, plasticizers, various additives, solvents, dehydrating agents and the like can be added and mixed according to the intended performance.

As the curing catalyst, an organic tin compound, a metal complex, a basic compound, an organic phosphoric acid compound and water (moisture in the air) can be used. Specifically, examples of the organotin compound include dibutyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate, stannous octylate, dibutyltin methoxide, dibutyltin diacetylacetate, dibutyltin diversate, and dibutyltin oxide. Examples of the metal complex include titanate compounds such as tetrabutyl titanate, tetraisopropyl titanate, and triethanolamine titanate; metal carboxylate such as lead octylate, lead naphthenate, nickel naphthenate, and cobalt naphthenate; and aluminum acetylacetonate complex. And metal acetylacetonate complexes such as vanadium acetylacetonate complex. Examples of the basic compound include γ-aminopropyltrimethoxysilane, aminosilanes such as γ-aminopropyltriethoxysilane, laurylamine, octadecylamine,
Alkylamines such as hexadecylamine, quaternary ammonium salts such as tetramethylammonium chloride and benzalkonium chloride, DABCO (registered trademark) series manufactured by Sankyo Air Products, DABCO B
L-series, linear or cyclic tertiary amines and quaternary ammonium salts containing a plurality of nitrogen atoms, such as 1,8-diazabicyclo [5.4.0] undec-7-ene. As the organic phosphoric acid compound, monomethyl phosphoric acid, di-n
-Butyl phosphoric acid, triphenyl phosphate and the like.

Examples of the tackifier resin include rosins, terpene resins, aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, aromatic hydrocarbon resins, phenolic resins, and coumarone indene resins.

Examples of the anti-sagging agent include anhydrous silica, fatty acid bisamide, hydrogenated castor oil and the like.

As the epoxy resin, bisphenol A
Epoxy resin, bisphenol F epoxy resin, novolak epoxy resin, epoxy resin obtained by glycidylation of primary amine compound or secondary amine compound, epoxy resin having heterocycle, alicyclic epoxy resin, hydrogenated bisphenol A epoxy resin , A urethane-modified epoxy resin, a hydantoin-type epoxy resin, a styrene-butadiene-styrene (SBS) rubber having an oxirane ring, a butadiene rubber having an oxirane ring, and the like, and one or more of these can be used.

As the epoxy resin, those having two or more oxirane rings and a molecular weight of 50 to 25,000 are usually used. Various alkyl glycidyl ethers, long-chain aliphatic glycidyl ethers, cresyl glycidyl ether, p
-Tert-butylphenyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether,
A cresol glycidyl ether, an alkylphenol glycidyl ether, a monoepoxysilane compound, a monoepoxy compound such as styrene oxide or cyclohexene oxide may be used. Other, EPK-207
(Trade name, manufactured by Shell Japan Co., Ltd.), silicate derivative containing epoxy group (trade name, manufactured by Mitsubishi Chemical Corporation, trade name: MSEP2, M
S51SGEP, etc., trade name of Kyoeisha Chemical Co., Ltd .: Epolite series (40E, 70P, 80MF, 100 series,
200 series, 400 series, 1500 NP, 1600, 300
2,4000, M-1230, FR-1500, etc.), Adeka Resin EP-4006 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.)
Etc. can also be used.

As the oligomer, polyethylene oligomer, liquid polypropylene, oligostyrene, liquid polychloroprene, liquid polyisoprene, liquid SBR, liquid NBR, liquid butyl rubber, liquid polyisobutylene, liquid polybutadiene, polyhydroxypolyolefin oligomer, α-methylstyrene Oligomers, phosphorus-containing styrene-α-methylstyrene oligomers, oligoester acrylates, and the like. Also, a naphthenic, aromatic, paraffinic or other process oil can be added for the purpose of adjusting viscosity or reducing tack.

Examples of the filler include calcium carbonate, various treated calcium carbonates, fumed silica, clay, talc, various balloons and the like.

As a plasticizer, dioctyl phthalate,
Phthalate esters such as dibutyl phthalate, and aliphatic carboxylic acid esters such as dioctyl adipate and dibutyl sebacate can be used.

Examples of the additives include pigments, titanate coupling agents, aluminum coupling agents and the like.

Any solvent may be used as long as it is compatible with the above composition and has a water content of 500 ppm or less.

Examples of the dehydrating agent include quicklime, magnesium oxide, orthosilicate, anhydrous sodium sulfate, zeolite, methylsilicate, ethylsilicate, vinylalkoxysilane, various alkylalkoxysilanes (commonly known as silane coupling agents) and the like.

[0063]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. Parts in the examples and comparative examples are based on mass.

Example 1 (1) KBM602 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., N-
Using 1 mol of β (aminoethyl) -γ-aminopropylmethyldimethoxysilane) and 2 mol of methyl acrylate, the mixture is reacted at 50 ° C. for 5 days to produce a product (product 1-1) (synthesis B). I got (2) 1 mol of the product 1-1, HMDI (hydride of 4,4'-diphenylmethane diisocyanate) (trade name: Dismodule W, manufactured by Sumitomo Bayer Urethane Co., Ltd.)
Was used under a nitrogen atmosphere at 50 ° C. with stirring for 5 hours to obtain a product (product 1-2) (synthetic product C). (3) 1 mol of product 1-2, triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyloxyphenyl) propionate] (trade name: Irganox 245, Nippon Ciba Geigy) Was used under a nitrogen atmosphere, and the mixture was reacted at 80 ° C. for 6 hours to obtain (Product 1-3) (synthetic product A). (4) 1 part of product 1-3, 100 parts of ESS-2420 (trade name; modified silicone resin, manufactured by Asahi Glass Co., Ltd.), and calcium carbonate (trade name: Shiraishika CCR, manufactured by Shiraishi Industry Co., Ltd.)
150 parts of diisodecyl phthalate (DIDP)
0 parts, anti-sagging agent (trade name: Disparon # 6500,
After mixing 10 parts of Kusumoto Kasei Co., Ltd., the mixture was heated and dehydrated at 110 ° C. for 2 hours and cooled to room temperature. 1 part of (basic catalyst) and 3 parts of KBM902 (trade name; γ-aminopropylmethyldimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.), and kneaded to obtain a resin composition (composition-1).
I got

(Comparative Example 1) ESS-2420 was added to 100
Parts, 150 parts of white luster CCR, 50 parts of DIDP, and 10 parts of Disparon # 6500, and then dehydrated by heating at 110 ° C. for 2 hours.
Parts, 1 part of laurylamine, 3 parts of KBM902 and 1 part of Irganox 245 were added and kneaded to obtain a resin composition.

(Example 2) (1) KBM903 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., γ-
1 mol of aminopropyltrimethoxysilane) and 1 mol of n-butyl methacrylate at 50 ° C.
The reaction was carried out for 0 days to obtain a product (product 2-1). (2) 1 mol of the product 2-1 and HXDI (hydride of xylylene diisocyanate) (trade name: Takenate 60)
0, manufactured by Takeda Pharmaceutical Co., Ltd.) at a ratio of 1 mol, and reacted under stirring at 50 ° C. for 8 hours under a nitrogen atmosphere to obtain a product (product 2-2). (3) 1 mol of the product 2-2, 2- [2-hydroxysiloxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole (trade name: Tinuvin 2
34, manufactured by Nippon Ciba Geigy Co., Ltd.) at a ratio of 0.9 mol, followed by reaction at 80 ° C. for 2 hours (product 2).
-3) was obtained. (4) 2 parts of the product 2-3, 50 parts of S-303 (trade name; modified silicone resin having a molecular terminal methyldimethoxysilyl type, manufactured by Kaneka Chemical Co., Ltd.), and S-203 (trade name; Kanebuchi) 50 parts of modified silicone resin of molecular terminal methyldimethoxysilyl type (manufactured by Chemical Industry Co., Ltd.) and 150 parts of white glossy CCR
Parts, 50 parts of DIDP and 10 parts of Dispalon # 6500
After mixing, the mixture was dehydrated by heating at 110 ° C. for 2 hours, cooled to room temperature, and then 1 part of Stan BL and 1 part of laurylamine were added.
Parts and 3 parts of KBM902 were added and kneaded to obtain a resin composition.

(Comparative Example 2) 50 parts of S-303, S-2
03 50 parts, white luster CCR 150 parts, DIDP 5
After mixing 0 parts and 10 parts of Disparon # 6500,
After dehydrating by heating at 110 ° C. for 2 hours and cooling to room temperature, 1 part of Stan BL, 1 part of laurylamine, 3 parts of KBM902 and 2 parts of Tinuvin 234 were added and kneaded to obtain a resin composition.

Example 3 (1) 1 mol of KBM902 and 1 mol of stearyl acrylate were reacted at 50 ° C. for 10 days to obtain a product (product 3-1). (2) 1 mol of the product 3-1 and 1 mol of norbornane diisocyanate are used at 50 ° C. in a nitrogen atmosphere at 8 ° C.
The reaction was carried out under stirring for a time to obtain a product (product 3-2). (3) 1 mol of the product 3-2, 2- (3,5-di-t-
Bis (1,2,2,6,6-pentamethyl-4-butyl-4-hydroxybenzyl) -2-n-butylmalonate
After mixing using 0.6 mol of piperidyl) (trade name: Tinuvin 144, manufactured by Ciba Geigy Japan), 9
The reaction was carried out at 0 ° C. for 2 hours to obtain (product 3-3). (4) 0.5 part of product 3-3, MA903 (trade name;
10 parts of modified silicone resin manufactured by Kanegafuchi Chemical Co., Ltd., E
40 parts of SS-2410 (trade name; modified silicone resin, manufactured by Asahi Glass Co., Ltd.), 50 parts of ESS-2420, and white luster C
CR 150 parts, DIDP 50 parts, Dispalon # 6
After mixing 10 parts of 500, the mixture was heated and dehydrated at 110 ° C. for 2 hours, cooled to room temperature, and then 1 part of Stan BL, 1 part of laurylamine and 3 parts of KBM902 were added and kneaded to obtain a resin composition. Was.

(Comparative Example 3) 10 parts of MA903, ESS
After mixing 40 parts of −2410, 50 parts of ESS-2420, 150 parts of white luster CCR, 50 parts of DIDP, and 10 parts of Disparon # 6500, the mixture was heated and dehydrated at 110 ° C. for 2 hours, and cooled to room temperature. 1 part of Stan BL, 1 part of laurylamine, 3 parts of KBM902, Tinuvin 14
4 was added and kneaded to obtain a resin composition.

Example 4 (1) KBM502 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., γ-
Methacryloxypropylmethyldimethoxysilane)
Mole, isobutylamine at a ratio of 1 mole,
For 7 days to obtain a product (product 4-1). (2) 2 mol of product 4-1, Sumidur N3200
(Product name; manufactured by Sumitomo Bayer Urethane Co., Ltd., triisocyanate, biuret skeleton) was used at a ratio of 1 mol, and the mixture was reacted under stirring in a nitrogen atmosphere at 50 ° C. for 8 hours to obtain a product (product 4-2). (3) 1 mol of the product 4-2, 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 259, Japan (Ciba Geigy) at a rate of 1.1 mol at 80 ° C. for 2 hours (product 4-
3) was obtained. (4) Bamboo rack P-28 (trade name; dehydrated by heating)
After mixing 400 parts of Polyol (produced by Takeda Pharmaceutical Co., Ltd.) and 60 parts of lysine triisocyanate, the mixture is reacted at 90 ° C. for 3 hours to prepare a urethane prepolymer, and an equivalent amount of isocyanate groups of the urethane prepolymer is formed. Compound 4-1 was added and reacted to obtain a base polymer. (5)
After mixing 5 parts of the product 4-3, 100 parts of the base polymer prepared in (4), 150 parts of white luster CCR, 50 parts of DIDP, and 10 parts of Disparon # 6500, the mixture is mixed at 110 ° C. for 2 hours. After heat dehydration and cooling to room temperature, 1 part of Stan BL, 1 part of laurylamine and 3 parts of KBM902 were added and kneaded to obtain a resin composition.

Example 5 (1) KBM802 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., γ-
1 mol of mercaptopropylmethyldimethoxysilane) and 1 mol of Dismodur W at 50 ° C.
For 3 days to obtain a product (product 5-1). (2) 1 mol of product 5-1 and 0.8 mol of tinuvin 234
The reaction was carried out at 80 ° C. for 2 hours to obtain a product (product 5-2). (3) 3 parts of product 5-2, 10 parts of MA908 (trade name; modified silicone resin manufactured by Kaneka Chemical Co., Ltd.), ESS
After mixing 40 parts of −2410, 50 parts of ESS-2420, 150 parts of white luster CCR, 50 parts of DIDP, and 10 parts of Disparon # 6500, the mixture was heated and dehydrated at 110 ° C. for 2 hours, and cooled to room temperature. One part of Stan BL, 1 part of laurylamine and 3 parts of KBM602 were added and kneaded to obtain a resin composition.

(Example 6) (1) KBE9007 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., γ
-Isocyanatopropyltriethoxysilane) at a ratio of 1 mol and Irganox 259 at a ratio of 1 mol.
The reaction was performed at 2 ° C. for 2 hours to obtain a product (product 6-1) (synthetic product A). (2) 4 parts of product 6-1; 10 parts of MA911 (trade name; modified silicone resin manufactured by Kaneka Chemical Co., Ltd.); ESS
After mixing 40 parts of −2410, 50 parts of ESS-2420, 150 parts of white luster CCR, 50 parts of DIDP, and 10 parts of Disparon # 6500, the mixture was heated and dehydrated at 110 ° C. for 2 hours, and cooled to room temperature. One part of Stan BL, 1 part of laurylamine and 3 parts of KBM602 were added and kneaded to obtain a resin composition.

Example 7 (1) KBM573 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., N-
1 mol of phenyl-γ-aminopropyltrimethoxysilane, HDI (hexamethylene diisocyanate)
(Product name: Dismodule H, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was used at a mole ratio of 1 mol and reacted at 30 ° C. for 3 days to obtain a product (product 7-1). (2) 1 mol of the product 7-1 is 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-
Butylanilino) -1,3,5-triazine (trade name:
Irganox 565, manufactured by Nippon Ciba Geigy).
The product was used at a ratio of 7 mol and reacted at 80 ° C. for 2 hours to obtain a product (product 7-2). (3) 2 parts of product 7-2, 10 parts of MA943 (trade name; modified silicone resin manufactured by Kaneka Chemical Co., Ltd.), ESS
After mixing 40 parts of −2410, 50 parts of ESS-2420, 150 parts of white luster CCR, 50 parts of DIDP, and 10 parts of Disparon # 6500, the mixture was heated and dehydrated at 110 ° C. for 2 hours, and cooled to room temperature. One part of Stan BL, 1 part of laurylamine and 3 parts of KBM602 were added and kneaded to obtain a resin composition.

Example 8 (1) 1 mol of n-butanol was added dropwise while stirring 1 mol of Dismodur W in a nitrogen atmosphere. (Product 8
-1) was obtained. (2) 1 mol of KBM602 and 1 mol of methyl acrylate
The reaction was carried out at room temperature for 2 days, and 1 mol of the product 8-1 was further added. The mixture was reacted at 50 ° C. for 3 days to obtain a product (product 8-2). (3) Under nitrogen atmosphere, 1 mol of the product 8-2 and 1 mol of Dismodur W were used and reacted at 50 ° C. for 5 hours to obtain a product (product 8-3). (4) 1 mol of product 8-3, Irganox 1010
Was used at a molar ratio of 1 and reacted at 80 ° C. for 2 hours to obtain a product (product 8-4). (5) 3 parts of product 8-4, 10 parts of MA440 (trade name; modified silicone resin manufactured by Kaneka Chemical Co., Ltd.), ESS
After mixing 40 parts of −2410, 50 parts of ESS-2420, 150 parts of white luster CCR, 50 parts of DIDP, and 10 parts of Disparon # 6500, the mixture was heated and dehydrated at 110 ° C. for 2 hours, and cooled to room temperature. One part of Stan BL, 1 part of laurylamine and 3 parts of KBM602 were added and kneaded to obtain a resin composition.

Example 9 (1) 1 mol of KBM602 and 1 mol of diethyl maleate
After reacting at room temperature for 3 days, 1 mol of methyl acrylate was further added and reacted at 50 ° C. for 7 days to obtain a product (product 9-1). (2) Under nitrogen atmosphere, 1 mol of the product 9-1 and 1 mol of isophorone diisocyanate (trade name: Dismodule I, manufactured by Sumitomo Bayer Urethane Co., Ltd.) are used at a ratio of 50 mol.
The reaction was carried out with stirring at 5 ° C. for 5 hours to obtain a product (product 9-2). (3) 1 mol of product 9-2, octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
After mixing propionate (trade name: Irganox 1076, manufactured by Nippon Ciba Geigy) at a ratio of 1 mol, 8
The reaction was carried out at 0 ° C. for 2 hours to obtain a product (product 9-3). (4) 1 part of product 9-3, 10 parts of MA430 (trade name; modified silicone resin manufactured by Kaneka Chemical Co., Ltd.), ESS
After mixing 40 parts of −2410, 50 parts of ESS-2420, 150 parts of white luster CCR, 50 parts of DIDP, and 10 parts of Disparon # 6500, the mixture was heated and dehydrated at 110 ° C. for 2 hours, and cooled to room temperature. One part of Stan BL, 1 part of laurylamine and 3 parts of KBM602 were added and kneaded to obtain a resin composition.

Example 10 (1) 1 mol of KBM903 and 1 mol of acrylonitrile were reacted at 50 ° C. for 3 days to obtain a product (product 10-1). (2) Using 1 mol of the product 10-1 and 1 mol of Dismodur W, the mixture was reacted under stirring at 50 ° C. for 5 hours in a nitrogen atmosphere to obtain a product (product 10-2). (3) 1 mol of product 10-2 was added to N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-
Hydrocinnamide (trade name: Irganox 1098,
After mixing under a nitrogen atmosphere using 0.4 mol of Nippon Ciba Geigy Co., Ltd., the mixture was reacted at 80 ° C. for 2 hours to obtain a product (product 10-3). (4) 1 part of the product 10-3, 10 parts of MA447 (trade name; modified silicone resin manufactured by Kaneka Chemical Co., Ltd.), ES
After mixing 40 parts of S-2410, 50 parts of ESS-2420, 150 parts of white luster CCR, 50 parts of DIDP, and 10 parts of Disparon # 6500, the mixture was heated and dehydrated at 110 ° C. for 2 hours, and then cooled to room temperature. And 1 part of Stan BL, 1 part of laurylamine and 3 parts of KBM602 were added and kneaded to obtain a resin composition.

Example 11 (1) 173 g of KBM903 and 102 g of propylene carbonate were reacted at 23 ° C. for 3 days to obtain a product (product 11-1). (2) Under a nitrogen atmosphere, 275 g of the product 11-1 and 250 g of Dismodular W, 24 hours at 20 ° C. under a nitrogen atmosphere.
The reaction was carried out under stirring for a time to obtain a product (product 11-2). (3) 525 g of the product 11-2 and 356 g of 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester (trade name: Irganox 1222, manufactured by Nippon Ciba Geigy) were mixed, and the mixture was added at room temperature for 24 hours. The reaction was carried out for an hour to obtain a product (product 11-3). (4) 0.5 part of product 11-3, 100 parts of ESS-2420, 150 parts of white luster CCR, 50 parts of DIDP
Parts, 10 parts of Disparon # 6500, and 1
After dehydrating by heating at 10 ° C. for 2 hours and cooling to room temperature, 1 part of Stan BL, 1 part of laurylamine, and 3 parts of KBM602 were added.
And kneaded to obtain a resin composition.

Example 12 (1) 1 mol of KBM602, 1 mol of acrylonitrile and 1 mol of 2-ethylhexyl acrylate were reacted at 40 ° C. for 7 days to produce a product (product 12-
1) was obtained. (2) In a nitrogen atmosphere, 1 mol of the product 12-1 and 1 mol of Dismodur W were used and reacted at 50 ° C. with stirring for 5 hours to obtain a product (product 12-2). (3) 1 mol of the product 12-2, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4)
(Hydroxybenzyl) benzene (trade name: Irganox 1330, manufactured by Nippon Ciba Geigy) was mixed at a ratio of 1 mol, and reacted at 80 ° C. for 2 hours to obtain a product (product 12-3). (4) 2 parts of product 12-3 and 10 parts of ESS-2420
After mixing 0 parts, 150 parts of white luster flower CCR, 50 parts of DIDP, and 10 parts of Dispalon # 6500, 110 ° C.
For 2 hours, and cooled to room temperature. Then, 1 part of Stan BL, 1 part of laurylamine and 3 parts of KBM602 were added and kneaded to obtain a resin composition.

Example 13 (1) 1 mol of KBM602 and 1 mol of propylene carbonate were reacted at room temperature for 2 days.
-Butyl acrylate was added in a molar ratio of 1 and reacted at 40 ° C. for 4 days to give the product (Product 13-
1) was obtained. (2) In a nitrogen atmosphere, 1 mol of the product 13-1 and 1 mol of Dismodur W were used and reacted at 23 ° C. with stirring for 24 hours to obtain a product (product 13-2).
(3) 1 mol of product 13-2, isooctyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl) propionate (trade name: Irganox 1135, manufactured by Nippon Ciba Geigy)
Was mixed at a ratio of 0.8 mol, and reacted at 23 ° C. for 2 days to obtain a product (product 13-3). (4) 3 parts of product 13-3 and 10 parts of ESS-2420
After mixing 0 parts, 150 parts of white luster flower CCR, 50 parts of DIDP, and 10 parts of Dispalon # 6500, 110 ° C.
For 2 hours, and cooled to room temperature. Then, 1 part of Stan BL, 1 part of laurylamine and 3 parts of KBM602 were added and kneaded to obtain a resin composition.

Example 14 (1) After reacting at 23 ° C. for 4 days using 1 mol of KBM602 and 1 mol of n-butyl acrylate,
P-Toluenesulfonyl isocyanate was added dropwise at a ratio of 1 mol, and after completion of the addition, the mixture was reacted at 50 ° C. for 1 day to obtain a product (product 14-1). (2) In a nitrogen atmosphere, 1 mol of the product 14-1 and 1 mol of Dismodur W were used and reacted under stirring at 23 ° C. for 24 hours to obtain a product (product 14-2). (3) 1 mol of product 14-2 was added to tris (3,5-di-
After using t-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by Nippon Ciba Geigy) at a ratio of 1.5 mol, 40
The reaction was carried out at 2 ° C. for 2 days to obtain a product (product 14-3). (4) 3 parts of product 14-3 and 10 parts of ESS-2420
After mixing 0 parts, 150 parts of white luster flower CCR, 50 parts of DIDP, and 10 parts of Dispalon # 6500, 110 ° C.
For 2 hours, and cooled to room temperature. Then, 1 part of Stan BL, 1 part of laurylamine and 3 parts of KBM602 were added and kneaded to obtain a resin composition.

Example 15 (1) In a nitrogen atmosphere, Dismodur I was added dropwise to 1 mol of n-hexylamine at room temperature so as to have a molar ratio of 1 mol. Thus, a product (product 15-1) was obtained. (2) After 1 mol of KBM602 and 1 mol of n-butyl acrylate were reacted at 23 ° C. for 4 days,
The product 15-1 was added dropwise so as to have a molar ratio of 1 mol. After the completion of the addition, the reaction was carried out at 50 ° C. for 1 day to obtain a product (product 1).
5-2) was obtained. (3) Under nitrogen atmosphere, 1 mol of product 15-2 and 1 mol of Dismodur W were used and reacted at 23 ° C. with stirring for 24 hours to obtain a product (product 15-3). (4) 1 mol of the product 15-3, 2- (3,5-di-t)
-Butyl-2-hydroxyphenyl) benzotriazole (trade name: Tinuvin 320, manufactured by Nippon Ciba Geigy)
Was used in a ratio of 1.3 mol and mixed under a nitrogen atmosphere.
The reaction was performed at 23 ° C. for 2 days to obtain a product (product 15-4). (5) 4 parts of product 15-4 and 10 parts of ESS-2420
After mixing 0 parts, 150 parts of white luster flower CCR, 50 parts of DIDP, and 10 parts of Dispalon # 6500, 110 ° C.
For 2 hours, and cooled to room temperature. Then, 1 part of Stan BL, 1 part of laurylamine and 3 parts of KBM602 were added and kneaded to obtain a resin composition.

Example 16 (1) Under a nitrogen atmosphere, 1 mol of di-n-butylamine was added to
Dismodule I was added dropwise at room temperature so as to have a molar ratio of 1 mol. After completion of the addition, the product was left at room temperature for 1 day to obtain a product (product 16-1). (2) After 1 mol of KBM602 and 1 mol of n-butyl acrylate were reacted at 23 ° C. for 4 days,
The product 16-1 was added dropwise so as to have a molar ratio of 1 mol. After the completion of the addition, the mixture was reacted at 50 ° C. for 1 day to obtain a product (product 1).
6-2) was obtained. (3) Product 16-2 under nitrogen atmosphere
Was used at a rate of 1 mol, and ethylene glycol dimethacrylate was used at a rate of 1 mol at 23 ° C. for 24 hours with stirring to obtain a product (product 16-3). (4) 1 mol of product 16-3 was added to bis (2,2,6,6
-Tetramethyl-4-piperidyl) sebacate (trade name: Tinuvin 770, manufactured by Ciba Geigy Japan)
The mixture was used in a molar ratio, mixed, and reacted at 23 ° C. for 2 days to obtain a product (product 16-4). (5) 5 parts of product 16-4 and 10 parts of ESS-2420
After mixing 0 parts, 150 parts of white luster flower CCR, 50 parts of DIDP, and 10 parts of Dispalon # 6500, 110 ° C.
For 2 hours, and cooled to room temperature. Then, 1 part of Stan BL, 1 part of laurylamine and 3 parts of KBM602 were added and kneaded to obtain a resin composition.

Example 17 (1) 1 mol of KBM903 and 1 mol of tripropylene glycol diacrylate were allowed to stand at 23 ° C. for 4 days to obtain a product (product 17-1). (2) 1 mol of product 17-1 and 0.1 mol of tinuvin 770.
The mixture was used at a ratio of 7 mol, mixed, and reacted at 23 ° C. for 2 days to obtain a product (product 17-2). (3) 4 parts of product 17-2 and 10 parts of ESS-2420
After mixing 0 parts, 150 parts of white luster flower CCR, 50 parts of DIDP, and 10 parts of Dispalon # 6500, 110 ° C.
For 2 hours, and cooled to room temperature. Then, 1 part of Stan BL, 1 part of laurylamine and 3 parts of KBM602 were added and kneaded to obtain a resin composition.

Example 18 (1) Under a nitrogen atmosphere, Dismodur I was added dropwise to 1 mol of n-valeric acid at room temperature so as to have a molar ratio of 1 mol. After completion of the dropwise addition, the mixture was left at 60 ° C. for 5 days. And the product (Product 18
-1) was obtained. (2) After 1 mol of KBM602 and 1 mol of n-butyl acrylate were reacted at 23 ° C. for 4 days,
The product 18-1 was added dropwise so as to have a molar ratio of 1 mol, and after completion of the addition, the mixture was reacted at 50 ° C. for 1 day to obtain a product (product 1).
8-2) was obtained. (3) In a nitrogen atmosphere, using 1 mol of P-2000 (trade name; polyether polyol, manufactured by Asahi Denka Co., Ltd.) and 2 mol of Dismodur W at a rate of 60 ° C. for 12 hours with stirring to obtain a product (Product 18-3) was obtained. (4) A product (product 18-4) is obtained by reacting with stirring at 23 ° C. for 24 hours using 1 mol of the product 18-2 and 1 mol of the product 18-3 in a nitrogen atmosphere. Was. (5) 1 mol of product 18-4, 2- (3,5-di-t)
-Butyl-2-hydroxyphenyl) -5-chlorobenzotriazole (trade name: Tinuvin 327, manufactured by Nippon Ciba Geigy) at a ratio of 1.5 mol, and after mixing,
The reaction was carried out at 40 ° C. for 2 days to obtain a product (product 18-5). (6) 4 parts of product 18-5 and 10 parts of ESS-2420
After mixing 0 parts, 150 parts of white luster flower CCR, 50 parts of DIDP, and 10 parts of Dispalon # 6500, 110 ° C.
For 2 hours, and cooled to room temperature. Then, 1 part of Stan BL, 1 part of laurylamine and 3 parts of KBM602 were added and kneaded to obtain a resin composition.

Example 19 (1) Under a nitrogen atmosphere, 1 mol of lauryl mercaptan was added to
Dismodule I was added dropwise at room temperature so as to have a molar ratio of 1 mol. After completion of the addition, the product was left at 80 ° C. for 1 day to obtain a product (product 19-1). (2) After 1 mol of KBM602 and 1 mol of n-butyl acrylate were reacted at 23 ° C. for 4 days,
The product 19-1 was added dropwise at a ratio of 1 mol, and after completion of the addition, the mixture was reacted at 50 ° C. for 1 day to obtain a product (product 1).
9-2) was obtained. (3) Under nitrogen atmosphere, 1 mol of product 19-2, 1 mol of hexamethylenediamine, Sumidur N3500
(Trade name; manufactured by Sumitomo Bayer Urethane Co., Ltd., triisocyanate: isocyanurate skeleton) at a ratio of 1 mol,
The reaction was allowed to proceed with stirring at 23 ° C. for 24 hours.
-3) was obtained. (4) 0.3 mol of product 19-3 and 1 mol of 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole (trade name: Tinuvin 328; manufactured by Nippon Ciba Geigy) After mixing, the mixture was reacted at 50 ° C. for 2 days to obtain a product (product 19-4). (5) 3 parts of product 19-4 and 10 parts of ESS-2420
After mixing 0 parts, 150 parts of white luster flower CCR, 50 parts of DIDP, and 10 parts of Dispalon # 6500, 110 ° C.
And then cooled to room temperature for 2 hours. 918
1 part (trade name; manufactured by Sankyoki Gosei Co., Ltd., silver catalyst), 1 part of laurylamine, and 3 parts of KBM602 were added and kneaded to obtain a resin composition.

Example 20 (1) 1 mol of KBM502 and 1 mol of tinuvin 770 were mixed and reacted at 50 ° C. for 10 days to produce a product (product 20-1) (synthetic product). D) was obtained. (2) 2 parts of product 20-1 and 10 parts of ESS-2420
After mixing 0 parts, 150 parts of white luster flower CCR, 50 parts of DIDP, and 10 parts of Dispalon # 6500, 110 ° C.
And then cooled to room temperature for 2 hours. 918
, 1 part of laurylamine and 3 parts of KBM602 were added and kneaded to obtain a resin composition (composition 2).

Example 21 (1) KBM603 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., N-
Using 1 mol of β (aminoethyl) -γ-aminopropyltrimethoxysilane) and 2 mol of n-butyl acrylate, the mixture was reacted at 50 ° C. for 3 days to obtain a product (product 21-1). . (2) Under nitrogen atmosphere, 1 mol of the product 21-1 and 1 mol of Dismodur W were used and reacted at 50 ° C. with stirring for 5 hours to obtain a product (product 21-2). (3) 1 mol of product 21-2, Irganox 311
After mixing at room temperature under a nitrogen atmosphere, the mixture was reacted at 80 ° C. for 6 hours to obtain a product (product 21-
3) was obtained. (4) 1 part of product 21-3, 90 parts of S810 (trade name; modified silicone resin manufactured by Kaneka Chemical Co., Ltd.), MA9
31 (trade name; modified silicone resin manufactured by Kanegafuchi Chemical Co., Ltd.), 10 parts of white luster CCR, 150 parts of DIDP, 5 parts of DIDP
After mixing 0 parts, the mixture was kneaded with a small three-roll mill to obtain composition 2.
1-4 were obtained. This composition is used as a main ingredient. (5) 1 part of Stan BL, 1 part of laurylamine, KB
3 parts for M602, 10 parts for white gloss CCR, 5 for DIDP
The parts were kneaded to obtain a composition 21-5. This composition is used as a curing agent. (6) A resin composition was obtained by mixing 300 parts of the main agent and 20 parts of the curing agent.

The resin compositions obtained in the above Examples and Comparative Examples were used as samples, applied to a stainless steel plate so as to have a thickness of 0.1 mm, and then subjected to accelerated exposure using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.). A test (black panel temperature: 63 ° C.) was performed to evaluate weather resistance. The evaluation was made by visually observing the time until the sample cracked. The results are shown in Table 1.

[0089]

[Table 1]

As is clear from Table 1, none of the resin compositions of the examples had cracks even after exposure for 350 hours or more, and the weather resistance was significantly improved as compared with the resin compositions of the comparative examples. Was.

[0091]

The resin composition of the present invention exhibits extremely excellent weather resistance as compared with a conventional organic silicone resin-based resin obtained by simply adding a deterioration inhibitor.

Claims (7)

[Claims] (1) The main chain is a polyoxyalkylene, and a reactive silicon group —SiX _a R
_3-a (R is a substituted or unsubstituted 1 to 10 carbon atoms.
A valent organic group, X is a hydroxy group or a hydrolyzable group,
a is 1, 2 or 3. ) And (2) an organic group (I) having an isocyanate group in the group, and a hydrolyzable group selected from an alkoxy group and an acetoxy group was directly bonded to a silicon atom. A silicon compound (compound (a)) and a secondary amino group,
Compound (synthetic compound A) obtained by reacting with a deterioration inhibitor (compound (b)) having a hydroxy group, a carboxy group, a mercapto group and / or a primary amino group.
A weatherable resin composition containing 1 to 100 parts by mass as a component. 2. The compound (a) has an organic group (II) having at least one group selected from a primary amino group, a secondary amino group and a (meth) acryloyl group in the group, and has an alkoxy group. And one or more compounds (compounds (c)) in which a hydrolyzable group selected from acetoxy and acetoxy groups are directly bonded to 1 to 10 silicon atoms, and an organic group (I
Less than two active hydrogen atoms belonging to a secondary amino group in one molecule obtained by reacting with an organic compound (compound (d)) capable of producing a compound having a secondary amino group by reacting with I) A compound in which the hydrolyzable group is directly bonded to 1 to 10 silicon atoms (synthetic compound B) or an organic group having one mercapto group or a secondary amino group in the group (III)
Having a hydrolyzable group selected from an alkoxy group and an acetoxy group directly bonded to one to three silicon atoms (compound (e)), and having two or more isocyanate groups in the molecule. The weather-resistant resin composition according to claim 1, which is a compound (synthesis C) obtained by reacting a compound (compound (f)). 3. The compound (c) is a compound (compound (c-1)) in which the organic group (II) is a group having one primary amino group, and the compound (d) is α 3. The weatherable resin composition according to claim 2, which is an α, β-unsaturated carbonyl compound (compound (g)), an α, β-unsaturated nitrile compound (compound (h)) and / or a carbonate compound (compound (i)). object. 4. The compound (c) wherein the organic group (II) is a group having two or more primary amino groups or secondary amino groups, or has one or more primary amino groups and secondary amino groups. A compound (compound (c-2)), wherein the compound (d) is the compound (g), the compound (h), the compound (i), or a compound having two or more isocyanate groups ( Compound (j)) and a compound having one or two active hydrogens capable of reacting with an isocyanate group in the molecule (compound (k)) and having less than two isocyanate groups in the molecule The weatherable resin composition according to claim 2, which is a compound (compound (l)) and / or a monoisocyanate compound (compound (m)). 5. The compound (k) is a monoalcohol,
The weatherable resin composition according to claim 4, which is a compound selected from a monoprimary amine, a monosecondary amine, a monocarboxylic acid, and a monothiol. 6. The compound (c) wherein the organic group (II) has a (meth) acryloyl group (compound (c-
3)), wherein the compound (d) is a mono-primary amine compound (compound (n)), or two or more primary amino groups or secondary amino groups, or one or more primary amino groups and secondary amino groups Reaction product of a compound having the formula (compound (o)) with the compound (g), the compound (h), the compound (i), the compound (l), or the compound (m) (compound (p)) 3. The weatherable resin composition according to claim 2, wherein 7. (1) The main chain is polyoxyalkylene, and a reactive silicon group —SiX _a R
_3-a (R is a substituted or unsubstituted 1 to 10 carbon atoms.
A valent organic group, X is a hydroxy group or a hydrolyzable group,
a is 1, 2 or 3. ), And (2) an organic group (IV) having a (meth) acryloyl group in the group, and a hydrolyzable group selected from an alkoxy group and an acetoxy group is directly bonded to a silicon atom. (Compound D) obtained by reacting a compound (compound (q)) bonded to a compound with a deterioration inhibitor (compound (r)) having a secondary amino group, a mercapto group and / or a primary amino group. A weatherable resin composition containing 0.1 to 30 parts by mass as a component.