JP2001262125A - Sealant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly weathering and delustering sealant composition capable of forming a highly weathering cured sealant surface stably low in luster even after storage without impairing the fundamental performance necessary for sealant. SOLUTION: This highly weathering and delustering sealant composition comprises (A) a crosslinkable silyl group-containing organic polymer, (B) a photocurable compound, (C) a compound capable of forming a primary and/or secondary amine when reacted with water, and optionally, furthermore, (D) a crosslinking catalyst, (E) antioxidant and/or ultraviolet light absorber, (F) an additive and (G) balloons >=100 μm in average size.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an unobtrusive, moisture-curable, highly weather-resistant matte sealing material composition which is particularly suitable for sealing high-quality exterior wall materials having a low surface gloss and a low gloss. Low-gloss, low-gloss, durable, hard-wearing, highly weather-resistant uneven surface that is especially suitable for sealing exterior wall materials with a solid image that mimics natural rough rock and has a solid image The present invention relates to a formable matte sealing material composition.

[0002]

2. Description of the Related Art Ceramic-based outer wall materials have rapidly spread as alternatives to conventional mortar finishing in terms of fire resistance, workability, and good appearance, and are becoming mainstream, particularly in single-family houses. In recent years, exterior wall materials with a calm and high-grade image have been painted by reducing the gloss of the surface of the exterior wall material to reduce the gloss, or the surface of the exterior wall material has been matted and sanded with sand Outer wall materials with a solid image imitating natural rough rocks with decorations and sandstone-like decorations imitating the unevenness of rocks have been used.

[0003] The joints of exterior wall materials coated with reduced surface gloss and matte, or sandstone with sanding decoration and surface irregularities in which the surface gloss is reduced and matted and sand is applied If you use a glossy or glossy sealing material on the joints of the exterior wall material imitating natural rough rocks by giving a tone decoration, the sealing material appears to be more floating than the exterior wall material, and the joint is conspicuous, The aesthetic features of the exterior wall material are reduced, and the overall appearance of the exterior wall of the building is impaired.
Therefore, for example, in Japanese Patent Application Laid-Open No. Hei 9-100408, an amine compound having a melting point of 10 to 200 ° C. is blended with a propylene oxide polymer having a hydrolyzable silyl group,
A room temperature curable composition having a matte surface after curing has been proposed. Japanese Patent Application Laid-Open No. Hei 10-251618 proposes a sealing material composition having a rough feeling, in which a balloon having an average particle diameter of 100 μm or more is mixed in the sealing material composition.

Recently, there has been a demand for a high-performance sealing material having high weather resistance and other physical properties, in addition to characteristics such as low surface gloss or matte sanding utilizing the aesthetic features of the outer wall material. It is getting. As a resin for a sealing material having high weather resistance, a composition in which a photocurable substance such as an unsaturated acrylic compound is mixed with a reactive organic silicon group-containing oxyalkylene polymer is known (Japanese Patent Application Laid-Open No. H05-1993). No. 65400, Japanese Patent Publication No. 62-2634
No. 9). However, when an amine compound or the like is blended into the sealing material composition containing such a photocurable substance for matting, the unsaturated group of the photocurable substance and the amino group of the amine compound react during storage, The matting effect of the cured surface of the sealing material by the amine compound is impaired, and the effect of improving the weather resistance by the unsaturated group of the photocurable substance is impaired. In particular, when an acrylic group-containing compound is used as the photocurable compound, the unsaturated group and the amino group of the amine compound react at an early stage, and the matting effect and the improvement of weather resistance immediately after the production of the sealing material composition. The effect is impaired. In addition, when a methacrylic group-containing compound is used, the unsaturated group and the amino group gradually react with each other, so that there is no problem immediately after the production of the sealing material composition, but the reaction proceeds during storage, and after the storage, the sealing material is removed. When used, there is a problem that the matting effect on the cured surface of the sealing material and the effect of improving weather resistance are impaired.

[0005] In addition, the method of blending the balloon with the sealing material composition is based on the fact that although the surface of the sealing material after curing has a rough feeling like dusting sand, irregularities of light are insufficient and irregular reflection of light is insufficient. The glossiness of the surface is still high and the gloss remains, and the outer wall material is used to remove the gloss of the surface and apply sanding-like decoration with sand and sandstone-like decoration that imitates the unevenness of rock, When used as a sealing material for exterior wall materials that have a solid image that resembles rough rocks, the sealing material appears to be more prominent than the exterior wall material, which also reduces the aesthetic features of the exterior wall material and, as a whole, the appearance of the building exterior wall There is a problem that it is impaired.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems and has excellent storage stability without impairing the basic performance required for a sealing material such as workability, modulus, and durability. Moisture-curing type that can form a stable surface of a cured sealing material that has a stable and low surface glossiness, is not glossy, has no surface contamination, has excellent weather resistance, and has excellent paint adhesion when a cured surface is applied. Sealant composition,
In addition to the above-mentioned properties, moisture having a rough appearance with relatively large irregularities such as sand dust, and having a sufficiently large diffused reflection of light, a low surface glossiness, and a dull cured surface sealing material surface. An object of the present invention is to provide a curable sealing material composition.

[0007]

In order to achieve the above object, the present invention provides a highly weather-resistant matte sealing material comprising the following components (A), (B) and (C). A composition. (A) Crosslinkable silyl group-containing organic polymer (B) Photocurable compound (C) Compound which reacts with water to form primary and / or secondary amine

[0008] The present invention is a highly weatherable matte sealing material composition characterized by comprising the following components (A), (B), (C), (D) and (E). (A) Crosslinkable silyl group-containing organic polymer (B) Photocurable compound (C) Compound which reacts with water to form primary and / or secondary amine (D) Crosslinking catalyst (E) Antioxidation Agent and / or UV absorber

The present invention provides a highly weatherable matte sealing material composition comprising the following components (A), (B), (C), (D), (E), and (F). It is. (A) Crosslinkable silyl group-containing organic polymer (B) Photocurable compound (C) Compound which reacts with water to form primary and / or secondary amine (D) Crosslinking catalyst (E) Antioxidation Agent and / or ultraviolet absorber (F) additive

In the present invention, the component (A) is preferably a polyoxyalkylene polymer containing a crosslinkable silyl group, an acrylic-modified polyoxyalkylene polymer containing a crosslinkable silyl group, and / or
Or each of the above high weather resistant matte sealing material compositions, which is a crosslinkable silyl group-containing methacryl-modified polyoxyalkylene polymer.

The present invention provides the above-mentioned high weather resistant matte sealing material composition, wherein the component (B) is an ethylenically unsaturated compound containing two or more double bonds in the molecule.

The present invention provides the above-mentioned high weather resistant matte sealing material composition wherein the component (C) is a ketimine compound, an enamine compound and / or an aldimine compound of a primary and / or secondary amine. Things.

[0013] The present invention provides a highly weatherable matte sealing material composition having an uneven surface forming surface, comprising a balloon having an average particle diameter of 100 µm or more, in addition to each of the above-mentioned high weatherable matte sealing material compositions. is there.

In the present invention, the balloon preferably has an average particle diameter of 200 to 400 μm and a volume concentration of the balloon in the sealing material composition of 10 to 25 vol%.
The above-mentioned high weather resistance matte sealing material composition having an uneven surface-forming surface.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The crosslinkable silyl group-containing organic polymer (A) in the present invention is an organic polymer containing one or more silyl groups, which forms a rubber-like cured product by forming a siloxane bond in the molecule to form a rubbery cured product. is there. Examples of such a crosslinkable silyl group-containing organic polymer include, for example, JP-A-52-739.
No. 98, JP-A-55-9669, JP-A-59-9669
JP-A-122541, JP-A-60-6747,
JP-A-61-233043, JP-A-63-112
642, JP-A-3-79627, JP-A-4
-283259, JP-A-5-70531,
JP-A-5-287186, JP-A-11-8057
No. 1, Japanese Unexamined Patent Application Publication No. 11-116763, Japanese Unexamined Patent Application Publication No.
JP-A-1-130931 can be mentioned. Specific examples of the crosslinkable silyl group-containing organic polymer in the present invention include polyoxyalkylenes containing one or more crosslinkable silyl groups in the molecule, and main chains each of which may contain an organosiloxane. Examples thereof include polymers, vinyl-modified polyoxyalkylene polymers, vinyl polymers, polyester polymers, acrylate polymers, methacrylate polymers, and copolymers and mixtures thereof. A crosslinkable silyl group is
From the viewpoint of the curability of the sealing material, the physical properties after curing, and the like, it is preferable that 1 to 5 are contained in the molecule. Further, the crosslinkable silyl group is preferably one represented by the following general formula, which is easily crosslinked and easily produced.

[0016]

Embedded image (In the formula, R is a hydrocarbon group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or 7 to 2 carbon atoms.
An aralkyl group of 0 is preferred, and a methyl group is most preferred. The reactive group represented by X is a halogen atom, a hydrogen atom,
Hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, a mercapto group, a group selected from an alkenyloxy group and an aminooxy group,
When X is plural, X may be the same group or different groups. Among them, X is preferably an alkoxy group, and most preferably a methoxy group. a is an integer of 0, 1 or 2, and 1 is most preferred. )

The main chain of the crosslinkable silyl group-containing organic polymer is
From the viewpoint of physical properties such as tensile adhesion and modulus after curing, a polyoxyalkylene polymer and / or a vinyl-modified polyoxyalkylene polymer, which may contain an organosiloxane, is preferable, and contains an organosiloxane. And a polyoxypropylene polymer, an acryl-modified polyoxypropylene polymer, and / or a methacryl-modified polyoxypropylene polymer.

The above-mentioned vinyl-modified polyoxyalkylene polymer containing one or more crosslinkable silyl groups in the molecule and optionally containing an organosiloxane is one in the molecule.
In the presence of a polyoxyalkylene polymer which may contain an organosiloxane, which contains one or more crosslinkable silyl groups, one kind of radical polymerization is carried out by a usual radical polymerization method such as addition of a radical polymerization initiator or ultraviolet irradiation. Alternatively, it can be obtained by polymerizing two or more kinds of vinyl monomers (JP-A-59-78223, JP-B-2-42).
No. 367 is cited as a reference, but is not limited thereto. The vinyl monomer is a compound having one or more polymerizable unsaturated bonds in the molecule, for example, ethylene, propylene, isobutylene,
Butadiene, chloroprene, vinyl chloride, vinylidene chloride, acrylic acid, methacrylic acid, vinyl acetate, acrylonitrile, styrene, chlorostyrene, 2-methylstyrene, divinylbenzene, methyl acrylate, ethyl acrylate, isobutyl acrylate, 2-acrylate Ethylhexyl, 2-hydroxyethyl acrylate, benzyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid 2
-Hydroxyethyl, benzyl methacrylate, glycidyl methacrylate, acrylamide, methacrylamide, n-methylol acrylamide, ethoxylated phenol acrylate, ethoxylated paracumyl phenol acrylate, ethoxylated nonyl phenol acrylate, propoxylated nonyl phenol acrylate, 2-
Ethylhexyl carbitol acrylate, N-vinyl-2-pyrrolidone, isobornyl acrylate, ethoxylated bisphenol F diacrylate, ethoxylated bisphenol A diacrylate, ethoxylated isocyanuric acid diacrylate, tripropylene glycol diacrylate, pentaerythritol diacrylate mono Stearate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, ethoxylated isocyanuric acid triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, dipenta Erythritol pentaacrylate, dipentaery Litol hexaacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, polyurethane diacrylate, ω-carboxy-polycaprolactone monoacrylate, phthalic acid monohydroxyethyl acrylate, acrylic acid dimer, 2-hydroxy-3-phenoxypropyl acrylate, Polyester polyacrylate, 1,6-hexanediol diacrylate, 2-
(2-ethoxyethoxy) ethyl acrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, lauryl acrylate, 2-phenoxy acrylate, isodecyl acrylate, isooctyl acrylate, tridecyl acrylate, caprolactone acrylate, zinc diacrylate, 1,3-butanediol Diacrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, propoxylated neopentyl glycol diacrylate, propoxylated glycerin triacrylate, ethoxylated pentaerythritol tetraacrylate, penta Acrylate ester, tetrahydrofurfuryl methacrylate , Cyclohexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, polypropylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol Dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butanediol dimethacrylate, ethoxylated bisphenol A dimethacrylate, zinc dimethacrylate, trimethylolpropane trimethacrylate, and the following chemical formula And the like, but are not limited thereto. Not shall.

[0019]

Embedded image The vinyl monomer is used in an amount of 0.1 to 1000 parts by weight, more preferably 1 to 200 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer which may contain an organosiloxane. preferable. In addition, the vinyl-modified polyoxyalkylene polymer containing one or more crosslinkable silyl groups in the molecule and optionally containing the organosiloxane includes one or more crosslinkable silyl groups in the molecule. A crosslinkable silyl obtained by introducing a crosslinkable silyl group into a polyoxyalkylene polymer which may contain an organosiloxane, and a polymer obtained by polymerizing one or more of the vinyl monomers. What blended with the group containing vinyl polymer can also be used.

In the present invention, the number average molecular weight of the crosslinkable silyl group-containing organic polymer is 1,000 or more, especially 6,000 to 6,000.
Those having a molecular weight distribution of 30,000 having a narrow molecular weight distribution are easy to handle because the viscosity before curing is low, and physical properties such as strength, elongation and modulus after curing are suitable.

In the present invention, the photocurable compound (B) used for improving the weather resistance is a compound having at least one group in the molecule which is reactively cured by light. A vinyl monomer, urethane acrylate, urethane methacrylate, or polyester acrylate, which is used for modifying a polyoxyalkylene polymer which may contain an organosiloxane, which contains a crosslinkable silyl group in the molecule. , Polyester methacrylate, polyether acrylate, polyether methacrylate and other monomers and oligomers, or
Partially hydrolyzed condensate of a compound having a polymerizable unsaturated group and a crosslinkable silyl group in the molecule, or polyvinyl cinnamate, azide resin, etc., among them, the effect of enhancing weather resistance From the viewpoint of preventing surface contamination and the like, ethylenically unsaturated compounds containing two or more double bonds in the molecule are preferable, and acrylic compounds such as acrylic acid compounds, methacrylic acid compounds, acrylamide, methacrylamide, and acrylonitrile are further preferred. Compound with a molecular weight of 10,000
The monomers and oligomers having an average molecular weight of not more than 00 are preferable, and an acryloyl group or a methacryloyl group has an average of 2 or less per molecule.
Those containing more than one are preferred. The component (B) is used in an amount of 0.1 to 100 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the crosslinkable silyl group-containing organic polymer in order to improve physical properties and weather resistance after curing. It is preferable to use it in the range.

The compound (C) which reacts with water to form a primary and / or secondary amine in the present invention is, for example, easily available raw materials, storage stability, and reactivity with water. In view of the above, ketimine compounds, enamine compounds, and / or aldimine compounds of primary and / or secondary amines can be preferably exemplified. These ketimine compounds, enamine compounds, and aldimine compounds can be obtained by a dehydration reaction of ketones or aldehydes with primary and / or secondary amines, respectively. Examples of the ketones include methyl ethyl ketone, methyl isopropyl ketone, methyl tert-butyl ketone,
2-pentanone, 3-pentanone, 2-hexanone,
-Methyl-2-pentanone, 2-heptanone, 4-heptanone, aliphatic ketones such as diisopropyl ketone and diisobutyl ketone, aromatic ketones such as propiophenone and benzophenone, and cyclic rings such as cyclopentanone, cyclohexanone and methylcyclohexanone Examples include ketones, β-dicarbonyl compounds such as ethyl acetoacetate, and the like, and examples of aldehydes include, but are not limited to, butyraldehyde, isobutyraldehyde, and hexylaldehyde. Among these, 4-methyl-2-pentanone is preferable from the same point as described above. Primary and / or secondary amines have a melting point of 35
C. or more or those containing one or more nitrogen atoms and two or more nitrogen atom-bonded active hydrogens in the molecule reduce the surface glossiness of the cured product of the sealing material of the present invention, and the surface matting ability Is large, so when used for sealing exterior wall materials with matte surface, the joint of the ceiling is not noticeable,
It is preferable because the characteristic appearance of the outer wall material is not impaired. As the primary amine, as a monoamine, butylamine, hexylamine, heptylamine, 2-ethylhexylamine, octylamine, 3-methoxypropylamine,
Examples thereof include tetradecylamine, pentadecylamine, cetylamine, stearylamine, trimethylcyclohexylamine, benzylamine, and aniline. Examples of the diamine include ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, and 1,4. -Diaminobutane, hexamethylenediamine, 1,7-diaminoheptane, trimethylhexamethylenediamine,
1,8-diaminooctane, 1,9-diaminononane,
1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,
15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18
Diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, 1,21-diaminohenticosan, 1,22-diaminodocosan, 1,
23-diaminotricosan, 1,24-diaminotetracosane, isophoronediamine, diaminodicyclohexylmethane, 3,9-bis (3-aminopropyl) -2,
4,8,10-tetraoxaspiro (5,5) undecane, xylenediamine, phenylenediamine, diaminodiphenylmethane, diaminodiethylphenylmethane,
Polyoxyethylenediamine, polyoxypropylenediamine and the like can be mentioned, and poly (amine) can be tri (methylamino) hexane and the like. Examples of the secondary amine include monoamines such as dilaurylamine, distearylamine and methyllaurylamine, N, N'-dilaurylpropylamine, N, N'-
Diamines such as distearylbutylamine, N-butyl-N'-laurylethylamine, N-butyl-N'-laurylpropylamine and N-lauryl-N'-stearylbutylamine can be mentioned. Other amines include N-lauryl propylene diamine, N-stearyl propylene diamine and the like.
Examples of the primary and secondary mixed polyamines include diethylenetriamine, triethylenetetramine, and methylaminopropylamine. Of these, the primary amines stearylamine and hexamethylenediamine are particularly preferred. If the melting point is less than 35 ° C,
Heat resistance, easy to soften especially at high temperature in summer, melting point 100
If the temperature is higher than 0 ° C., the surface of the sealing material is hard and brittle, and the elasticity, which is a basic characteristic of the sealing material, is easily lost. Therefore, primary and / or secondary amines have a melting point of 35 ° C. or more, especially 40 to 100 ° C. Are preferred. Component (C)
In order to remarkably reduce the gloss and gloss of the cured surface of the sealing material, a primary and / or secondary amine produced by reacting with water is added to 100 parts by weight of a crosslinkable silyl group-containing organic polymer. It is preferably used in an amount of 0.1 to 20 parts by weight, especially 0.5 to 10 parts by weight. Reacts with water first
The use of a compound that produces a secondary and / or secondary amine and a photocurable compound also has the effect of eliminating stickiness of the surface after curing of the sealing material and preventing contamination due to adhesion of dust and the like.

The (D) cross-linking catalyst in the present invention is a catalyst for cross-linking (curing) the cross-linkable silyl group-containing organic polymer, and specific examples include organometallic compounds and amines. Organotin compounds having excellent crosslinking rates are preferred. This organic tin compound is specifically, stannas octoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin distearate, dioctyltin Examples thereof include dilaurate and dioctyltin diversate, and among these, dibutyltin diacetylacetonate is most preferable because it is a liquid having a high crosslinking rate, a relatively low toxicity, and a low luminescent property. Component (D) is used in an amount of 0.1 to 10 parts by weight, particularly 0.5 to 5 parts by weight, based on 100 parts by weight of the crosslinkable silyl group-containing organic polymer, in view of the crosslinking speed, the physical properties of the cured product, and the like. Is preferred.

The (E) antioxidant and / or ultraviolet absorber in the present invention is used to prevent the cured sealing material from oxidizing or light deteriorating and to improve the weather resistance. Examples thereof include hindered amine-based and hindered phenol-based antioxidants, benzotriazole-based, triazine-based, benzophenone-based, and benzoate-based ultraviolet absorbers, and the like. One or more selected from these are used. Is done. Examples of the hindered amine antioxidant include N, N ', N ", N""
-Tetrakis- (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1 , 10-Diamine, dibutylamine ・ 1,
3,5-triazine.N, N'-bis- (2,2,6,
Polycondensate of 6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine.N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, 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}], dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1
Polymer of piperidine ethanol, bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidyl) decandioate, reaction product of 1,1-dimethylethyl hydroperoxide and octane (70
%)]-Polypropylene (30%), bis (1,2,2)
2,6,6-pentamethyl-4-piperidyl) [[3,
5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate, methyl 1,2,2
2,6,6-pentamethyl-4-piperidyl sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4 -Piperidyl) sebacate, 1- [2- [3
-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,
6,6-tetramethylpiperidine, 8-acetyl-3-
Dodecyl-7,7,9,9-tetramethyl-1,3,8
-Triazaspiro [4.5] decane-2,4-dione; and the like, but is not limited thereto.
As hindered phenolic antioxidants, for example,
Pentaeristol-tetrakis [3- (3,5-di-
tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene-bis [3- (3,5-di-
tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert)
-Butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [3-
(3,5-di-tert-butyl-4-hydroxyphenylpropioamide), 3,5-bis (1,1-dimethylethyl) -4-hydroxyC7-benzenepropanoate
C9 side chain alkyl ester, 2,4-dimethyl-6-
(1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ′,
3 ", 5,5 ', 5" -hexane-tert-butyl-
4-a, a ', a "-(mesitylene-2,4,6-tolyl) tri-p-cresol, calcium diethylbis [[[3,5-bis- (1,1-dimethylethyl) -4
-Hydroxyphenyl] methyl] phosphonate], 4,
6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-ter
t-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-te
rt-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione,
The reaction product of N-phenylbenzeneamine and 2,4,4-trimethylpentene, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5
-Triazin-2-ylamino) phenol and the like, but are not limited thereto. Examples of the ultraviolet absorber include 2,4-di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) phenol and 2- (2H-benzotriazol-2-yl) -4,6- Di-tert-pentylphenol, 2
-(2H-benzotriazol-2-yl) -4-
(1,1,3,3-tetramethylbutyl) phenol,
Methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product, 2- (2H-benzotriazol-2-yl) Benzotriazole ultraviolet absorbers such as -6- (linear and side chain dodecyl) -4-methylphenol;
(4,6-diphenyl-1,3,5-triazine-2-
Ill) -5-[(hexyl) oxy] -phenol and other triazine-based ultraviolet absorbers, octabenzone and other benzophenone-based ultraviolet absorbers, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl Examples include benzoate-based ultraviolet absorbers such as -4-hydroxybenzoate, but are not limited thereto.
Component (E) is used in an amount of 0.1 to 10 parts by weight, especially 0.5 to 5 parts by weight, based on 100 parts by weight of the crosslinkable silyl group-containing organic polymer in order to improve the weather resistance of the cured sealing material. It is preferred to use.

The highly weatherable matte sealing material composition of the present invention further comprises a coupling agent, a plasticizer, a filler, a thixotropic agent, a storage stability improving agent (dehydrating agent), a coloring agent, and if necessary. An additive (F) such as a radical polymerization initiator can be blended and used. Of these, a coupling agent, a thixotropic agent, a plasticizer and / or a filler are preferably used in the present invention in order to improve adhesion, increase the amount of the base polymer, reinforce, prevent dripping, and the like.

Examples of the coupling agent include silane-based, aluminum-based, and zirco-aluminate-based coupling agents. Among them, silane-based coupling agents are preferable because of their excellent adhesiveness. As this silane coupling agent, specifically, N- (2-aminoethyl) 3
-Aminopropylmethyldimethoxysilane, N- (2-
Low-molecular compounds having an alkoxysilyl group and having a molecular weight of 500 or less, preferably 400 or less, such as aminoethyl) 3-aminopropyltrimethoxysilane and N- (2-aminoethyl) 3-aminopropylmethylmethoxysilane, are exemplified. it can.

Examples of the thixotropic agent include inorganic thixotropic agents such as colloidal silica and asbestos powder, and organic thixotropic agents such as organic bentonite, modified polyester polyols and fatty acid amides. Calcium and the like can be mentioned, and among them, fatty acid-treated calcium carbonate is preferable.

As the plasticizer, phthalic acid esters such as dioctyl phthalate (DOP), dibutyl phthalate and butyl benzyl phthalate are preferable. In addition, aliphatic dibasic acid esters, glycol esters, aliphatic esters, phosphoric acid Examples include esters, epoxy plasticizers, polyester plasticizers, polyethers, and polystyrenes.

Examples of the filler include calcium carbonate, clay, talc, slate powder, mica, kaolin, zeolite, and diatomaceous earth. Particles having a particle size of 1 to 100 μm are preferred, and calcium carbonate is more preferred.

As the radical polymerization initiator, component (B)
Peroxide or azo compound for polymerizing
Specific examples include benzoyl peroxide, benzoyl hydroperoxide, tert-butyl peroxide, azoisobutyronitrile, diisopropylperoxy-dicarbonate, and the like, and are used as necessary.

The amount of the component (F) is from 0 to 800 based on 100 parts by weight of the crosslinkable silyl group-containing organic polymer.
It is preferably in the range of 0 to 400 parts by weight. Of the additives, the coupling agent, the thixotropic agent, the plasticizer and / or the filler is used in an amount of 0 to 800 parts by weight, particularly 100 to 400 parts by weight, based on 100 parts by weight of the crosslinkable silyl group-containing organic polymer. preferable.

In the present invention, a balloon is further used in order to give the roughened appearance of the sealing material after curing, which has a low surface glossiness, is dull, and has relatively large irregularities such as sand. . By using a balloon, the photocurable compound, and a compound that reacts with water to produce a primary and / or secondary amine,
In addition to providing the appearance characteristics of matting and unevenness on the surface of the sealing material after curing, deterioration of workability (extrudability) of the sealing material composition can be prevented. This balloon has a hollow inside and an average particle size of 100 μm.
As described above, those having a thickness of 200 to 400 μm are preferably used. When the average particle diameter of the balloon is less than 100 μm, even if it is blended in a large amount, the viscosity of the composition is merely increased, and a rough feeling is not exhibited. On the other hand, when the thickness exceeds 400 μm, physical properties such as workability, modulus, and durability deteriorate.

As the material of the balloon, inorganic materials such as glass, shirasu and silica, phenol resin,
Examples include, but are not limited to, organic materials such as urea resin, polystyrene, and saran, and include a combination of an inorganic material and an organic material, or lamination to form a plurality of layers. It may be made to be. The balloon may be made of the same material or a mixture of different kinds of balloons. Further, a balloon whose surface is processed or coated may be used, or a balloon whose surface is treated with various surface treating agents may be used. Specifically, for example, an organic balloon coated with calcium carbonate, talc, titanium oxide, or the like, or an inorganic balloon surface-treated with a silane coupling agent may be used. As the balloon in the present invention, from the viewpoint of low specific gravity and high strength, an inorganic balloon,
Particularly, a ceramic balloon is preferable.

The balloon is used in the sealing material composition at a volume concentration of 10 to 25 expressed by the following balloon volume concentration.
It is preferable to mix at a ratio of vol%, particularly 15 to 25 vol%. 10v volume concentration of balloon
ol%, the feeling of roughness is low, and 25 vol.
If the amount exceeds 1%, the viscosity of the sealing material composition becomes high, the workability tends to deteriorate, the modulus of the cured product also increases, and the basic performance of the sealing material tends to be impaired.

[0035]

(Equation 1)

In the sealing material composition of the present invention, each of the above components may be used alone or in combination of two or more.

[0037]

The present invention will be described below in more detail with reference to examples. Synthesis Example 1 500 g of heated and dissolved stearylamine (manufactured by Kao Corporation, Farmin 80, amine value 207) was placed in a heating device and a stirring vessel equipped with an ester tube, and then stirred.
Methyl-2-pentanone (MW = 100.2)
g was added. 130 g of toluene was further added thereto, and the mixture was heated and stirred at 110 to 150 ° C. for 3 hours, and 29.9 g of water was dehydrated by an ester tube. Then, the pressure was reduced to remove the excess 4-methyl-2-pentanone and toluene to obtain a ketimine compound of stearylamine.
This ketimine compound was a translucent liquid at room temperature.

Example 1 A crosslinkable silyl group-containing acrylic-modified polyoxypropylene polymer (Kanebuchi Chemical Industry Co., Ltd.) was placed in a kneading vessel equipped with a heating device.
200 g of MS polymer MSX911), vinyltrimethoxysilane (Silaace S21, manufactured by Chisso Corporation)
0) 10 g, dioctyl phthalate 130 g, hindered phenolic antioxidant: pentaeristol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Ciba Specialty Chemicals Co., Ltd.) Manufactured by Irganox 1010)
4 g, 250 g of fatty acid (surface) -treated calcium carbonate (manufactured by Maruo Calcium Co., Ltd., Calfine 200M) and 9 g of fatty acid amide (manufactured by Kao Corporation, fatty acid amide S) are charged and stirred to make the contents uniform. And mixed. Thereafter, dehydration under reduced pressure was performed at 110 ° C. for 1 hour, and after cooling, 10 g of trimethylolpropane trimethacrylate (SR-350, manufactured by Nippon Kayaku Co., Ltd.) and dibutyltin diacetylacetonate (Nitto Kasei, Neostan U)
-220), 2 g of N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane (Silaace S310, manufactured by Chisso Corp.), and 12 g of a stearylamine ketimine compound obtained in Synthesis Example 1 were added, followed by stirring. The mixture was mixed to prepare a sealant composition.

Example 2 In Example 1, pentaerythritol tetraacrylate (manufactured by Toagosei Co., Ltd., Aronix M-450) was used in place of trimethylolpropane trimethacrylate.
A sealing material composition was prepared in the same manner except that was used.

Example 3 In Example 1, a crosslinkable silyl group-containing polyoxypropylene polymer (manufactured by Asahi Glass Co., Ltd., E) was used instead of the crosslinkable silyl group-containing acrylic-modified polyoxypropylene polymer.
A sealing material composition was prepared in the same manner except that S-S3630) was used.

Example 4 In Example 2, a crosslinkable silyl group-containing polyoxypropylene polymer (manufactured by Asahi Glass Co., Ltd.,
A sealing material composition was prepared in the same manner except that S-S3630) was used.

Comparative Example 1 In Example 1, 10 g of stearylamine (manufactured by Kao Corporation, amine 80, amine value 207) was used without using trimethylolpropane trimethacrylate and instead of 12 g of the ketimine compound of stearylamine. A sealing material composition was prepared in the same manner except that it was used.

Comparative Example 2 In Example 1, stearylamine (manufactured by Kao Corporation) was used in place of 12 g of the ketimine compound of stearylamine.
A sealing material composition was prepared in the same manner except that 10 g of Farmin 80 and an amine value of 207) were used.

Comparative Example 3 In Example 2, stearylamine (manufactured by Kao Corporation) was used in place of 12 g of the ketimine compound of stearylamine.
A sealing material composition was prepared in the same manner except that 10 g of Farmin 80 and an amine value of 207) were used.

Comparative Example 4 In Example 3, stearylamine (manufactured by Kao Corporation) was used in place of 12 g of the ketimine compound of stearylamine.
A sealing material composition was prepared in the same manner except that 10 g of Farmin 80 and an amine value of 207) were used.

Comparative Example 5 In Example 4, stearylamine (manufactured by Kao Corporation) was used in place of 12 g of the ketimine compound of stearylamine.
A sealing material composition was prepared in the same manner except that 10 g of Farmin 80 and an amine value of 207) were used.

Synthesis Example 2 After heating and dissolving 116 g of hexamethylenediamine (MW = 116) in a stirring vessel equipped with a heating device and an ester tube, 4-methyl-2-pentanone (M
(W = 100.2). After further adding 80 g of toluene, the mixture was heated and heated at 110 to 150 ° C. for 3 hours.
The stirring was continued for an hour, and 36 g of water was dehydrated by an ester tube. Then, the pressure was reduced to remove the excess 4-methyl-2-pentanone and toluene to obtain a ketimine compound of hexamethylenediamine. This ketimine compound was a translucent liquid at room temperature.

Example 5 A crosslinkable silyl group-containing acrylic-modified polyoxypropylene polymer (Kanebuchi Chemical Industry Co., Ltd.) was placed in a kneading vessel equipped with a heating device.
MSX911) 200 g, vinyltrimethoxysilane (Chisso Corp., Sila Ace S210) 10 g,
130 g of dioctyl phthalate, hindered phenolic antioxidant: pentaeristol tetrakis [3-
(3,5-Di-tert-butyl-4-hydroxyphenyl) propionate] (Irganox 1010, manufactured by Ciba Specialty Chemicals Co., Ltd.), 4 g, fatty acid (surface) treated calcium carbonate (Maruo Calcium Co., Ltd.)
Manufactured by Calfine 200M) and 9 g of fatty acid amide (manufactured by Kao Corporation, fatty acid amide S) were stirred and mixed and dispersed until the contents became uniform. Thereafter, dehydration under reduced pressure was performed at 110 ° C. for 1 hour, and after cooling, polyester acrylate (Aronix M, manufactured by Toagosei Co., Ltd.)
8806, dibutyltin diacetylacetonate (Nitto Kasei Co., Ltd., Neostan U-22)
0) 2 g, 3 g of N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane (Silaace S310, manufactured by Chisso Corp.) and 4.3 g of a ketimine compound of hexamethylenediamine were added, followed by stirring, mixing and sealing. A material composition was prepared.

Example 6 In Example 5, polyester acrylate (Aronix M-8060, manufactured by Toagosei Co., Ltd., trifunctional or higher)
Was used in the same manner except that 3.1 g of a ketimine compound of hexamethylenediamine was used, and a sealing material composition was prepared.

Example 7 A crosslinkable silyl group-containing acrylic-modified polyoxypropylene polymer (Kanebuchi Chemical Industry Co., Ltd.) was placed in a kneading vessel equipped with a heating device.
MSX911) 200 g, vinyltrimethoxysilane (Chisso Corp., Sila Ace S210) 10 g,
130 g of dioctyl phthalate, hindered phenolic antioxidant: pentaeristol tetrakis [3-
(3,5-Di-tert-butyl-4-hydroxyphenyl) propionate] (Irganox 1010, manufactured by Ciba Specialty Chemicals Co., Ltd.), 4 g, fatty acid (surface) treated calcium carbonate (Maruo Calcium Co., Ltd.)
Manufactured by Calfine 200M) and 9 g of fatty acid amide (manufactured by Kao Corporation, fatty acid amide S) were stirred and mixed and dispersed until the contents became uniform. Thereafter, dehydration under reduced pressure was performed at 110 ° C. for 1 hour, and after cooling, polyester acrylate (Aronix M, manufactured by Toagosei Co., Ltd.)
8806, dibutyltin diacetylacetonate (Nitto Kasei Co., Ltd., Neostan U-22)
0) 2 g, 3 g of N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane (Silaace S310, manufactured by Chisso Corporation), 4.3 g of a ketimine compound of hexamethylenediamine, ceramic balloon (manufactured by Taiheiyo Cement Corporation) , E-SPHERESSL350, average particle size 250 μm), and stirred and mixed to prepare a sealing material composition.

Example 8 In Example 7, a polyester acrylate (manufactured by Toagosei Co., Ltd., Aronix M-8060, trifunctional or higher) was used.
Was used in the same manner except that 3.1 g of a ketimine compound of hexamethylenediamine was used, and a sealing material composition was prepared.

Comparative Example 6 A sealing material composition was prepared in the same manner as in Example 5 except that the ketimine compound of polyester acrylate and hexamethylenediamine was not used.

Comparative Example 7 A sealing material composition was prepared in the same manner as in Example 5 except that no polyester acrylate was used and that instead of 4.3 g of the ketimine compound of hexamethylenediamine, 2 g of hexamethylenediamine was used. Prepared.

Comparative Example 8 In Example 5, instead of 4.3 g of the ketimine compound of hexamethylenediamine, hexamethylenediamine 2 was used.
A sealing material composition was prepared in the same manner except that g was used.

Comparative Example 9 A sealing material composition was prepared in the same manner as in Example 7, except that the ketimine compound of polyester acrylate and hexamethylenediamine was not used.

Comparative Example 10 A sealing material composition was prepared in the same manner as in Example 7 except that polyester acrylate was not used and 2 g of hexamethylene diamine was used instead of 4.3 g of the ketimine compound of hexamethylene diamine. Prepared.

Comparative Example 11 In Example 7, instead of 4.3 g of the ketimine compound of hexamethylenediamine, hexamethylenediamine 2 was used.
A sealing material composition was prepared in the same manner except that g was used.

[Performance Test] (1) Surface Characteristics The obtained sealing material composition (immediately after production and after storage at 50 ° C. for 10 days) was cured into a sheet, and was cured at 23 ° C. and 50 ° C.
After curing at 7% relative humidity for 7 days, a sheet having a thickness of 5 mm was prepared. The smoothness and gloss of the surface of the sheet were visually determined and the stickiness of the surface was determined by finger touch, and the surface gloss was measured using a 60-degree specular gloss meter. The smaller the numerical value of the surface gloss, the lower the light reflectance, indicating that the surface gloss is reduced. Weather resistance is JIS K626
6: Using a sunshine weatherometer according to 1996, the state of the surface of the sealing material after 1000 hours, 2000 hours, 3000 hours, 5000 hours, and 7000 hours was visually determined. Judgment criteria: ○: No hair crack on sealing material surface ×: Many hair cracks on sealing material surface (2) Extrudability JIS A1439: 1997 “Extrusion using a 4.14 test cartridge” in “Testing method for building sealing material” Test (measuring temperature 23 ° C.). (3) Slump Slump (longitudinal) was measured (measuring temperature 23 ° C.) in accordance with “4.1 Slump test” of JIS A1439: 1997 “Testing method of building sealing material”. (4) Tensile Adhesion A test was conducted in accordance with JIS A1439: 1997 "4.21 Tensile Adhesion Test" of "Test Method for Building Sealing Material" (test temperature 23 ° C). The test piece was prepared by using a slate as a primer (OP2531, Auto Chemical Industry Co., Ltd.).
The sealing material composition was cast and the test piece after casting was placed at 23 ° C. and 50% relative humidity for 14 days at 30 ° C. for 1 day.
Cured for 4 days. (5) Modulus 50% tensile stress (M50) is less than 24,
24 or more were evaluated as x. (6) Adhesion of top coat paint Use a slate plate with a thickness of 5 mm, depth 5 mm, width 70
mm, a space having a length of 150 mm, a sealing material composition was poured into the space, an extra sealing material was scraped off with a spatula, and the flattened surface was cured at 23 ° C. and 50% relative humidity for 3 days. . Then, a water-based acrylic paint (Nippon Paint Co., Ltd., tile rack water-based top super white) was applied to the surface of the cured sealing material, and cured at the above temperature and humidity for 14 days to prepare a test body. After curing, the test specimens were tested for adhesion of the topcoat paint at a gap of 2 mm and 25 squares in accordance with JIS K5400: 1990, "8.5 Adhesion, base tape method" in "General Paint Test Methods". It was measured. The larger the value of the molecule, the better the adhesion of the paint. (7) Contamination Using a slate plate with a thickness of 5 mm, a depth of 5 mm and a width of 25
mm, a joint having a length of 150 mm, a sealing material composition was poured into the joint, an excess sealing material was scraped off with a spatula, and the surface was flattened at 23 ° C. and 50% relative humidity for 3 days. The specimen was cured and prepared. Black silica sand (particle size: 70 to 110 μm) was sprinkled on the surface of the cured test specimen, the test specimen was immediately turned over, and the bottom was patted lightly with a hand to drop excess black silica sand. The state of the black silica sand (dirt) remaining on the surface was visually observed to determine the contamination after curing. Another cured specimen was placed in a thermostat at 70 ° C., heated for 1 day, 2 days, and 5 days, taken out of the thermostat, and sprinkled with black silica sand in the same manner to determine the contamination.
Another test specimen after curing was exposed outdoors for 6 months and sprinkled with black silica sand in the same manner to determine the contamination. Judgment criteria ○: A clean state without black silica sand adhered to the cured surface of the sealing material ×: A large amount of black silica sand adhered to the cured surface of the sealing material and stained black The measurement results of each of the above performances are shown together with the raw material composition. 1, 2,
3 and 4 collectively show.

[0059]

[Table 1]

[0060]

[Table 2]

[0061]

[Table 3]

[0062]

[Table 4]

[0063]

As described above, the sealing material composition of the present invention has excellent storage stability and remarkable weather resistance without impairing basic properties required for the sealing material such as workability, modulus and durability. High, low surface gloss, no gloss and no surface contamination, and a cured sealing material with excellent adhesion to paint when the cured surface is painted, or with a roughened surface on the cured surface in addition to the above properties Since the surface of the material can be formed stably even after storage of the composition, it is particularly suitable for sealing an outer wall material having a low surface gloss or an outer wall material having a low surface gloss and imitating natural rough rock. When used, the joint of the sealing material is inconspicuous, does not reduce the characteristic aesthetics of the outer wall material, and has various properties such as workability, modulus, and durability. Therefore, for the first time according to the present invention, a high weather resistant matte sealing material composition and a high weather resistance capable of forming a building outer wall having a calm and high-grade image as a whole without impairing the basic performance as a sealing material It has become possible to provide a matte sealing material composition having an uneven surface forming property. Further, the high weather resistant matte sealing material composition and the high weather resistance uneven surface forming matte sealing material composition of the present invention can be used in places where high weather resistance and matte or in addition to the above, uneven surface formation is required. If it is used, it can be used not only for the joints of the ceramic outer wall material, but also for various waterproof sealings for buildings, automobiles, civil engineering, and the like.

Continued on the front page. (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08L 101/10 C08L 101/10 (72) Inventor Takanori Onoda 2044 No. 6 Kaminaki, Chiyoda-cho, Shinji-gun, Ibaraki Pref. Auto Chemical Industry Inside the Technical Research Institute Co., Ltd. (72) Osamu Takeda Inventor 2044 No. 6, Kamiinakichi, Chiyoda-cho, Niigata-gun, Ibaraki Prefecture F-term in the Technical Research Laboratory, Auto Chemical Industry Co., Ltd. 4H017 AA04 AA24 AA31 AA39 AB01 AB15 AC04 AC08 AC16 AD05 AD06 AE03 4J002 BC03X BD10X CC03X CC16X CH05W DJ008 DJ018 DL008 EE039 EF046 EH119 EJ019 EJ029 EJ049 EN027 EN037 EN038 EN039 EN047 EN048 EP016 ER006 EU079 EU179 EU189 EV039 EW119 EZ018 FA10X FA108 FD010 GFD020 FD059 FD0200

Claims (8)

[Claims] 1. A highly weatherable matte sealing material composition comprising the following components (A), (B) and (C). (A) Crosslinkable silyl group-containing organic polymer (B) Photocurable compound (C) Compound which reacts with water to form primary and / or secondary amine 2. A highly weatherable matte sealing material composition comprising the following components (A), (B), (C), (D), and (E). (A) Crosslinkable silyl group-containing organic polymer (B) Photocurable compound (C) Compound which reacts with water to form primary and / or secondary amine (D) Crosslinking catalyst (E) Antioxidation Agent and / or UV absorber 3. A highly weatherable matte sealing material composition comprising the following components (A), (B), (C), (D), (E), and (F). (A) Crosslinkable silyl group-containing organic polymer (B) Photocurable compound (C) Compound which reacts with water to form primary and / or secondary amine (D) Crosslinking catalyst (E) Antioxidation Agent and / or ultraviolet absorber (F) additive 4. The composition according to claim 1, wherein the component (A) is a polyoxyalkylene polymer having a crosslinkable silyl group, an acrylic-modified polyoxyalkylene polymer having a crosslinkable silyl group, and / or a methacryl-modified polyoxyalkylene polymer having a crosslinkable silyl group. The high weather resistant matte sealing material composition according to any one of claims 1 to 3, which is a coalesced product. 5. The high weather resistant mat according to claim 1, wherein the component (B) is an ethylenically unsaturated compound having two or more double bonds in a molecule. Sealant composition. 6. The composition according to claim 5, wherein the component (C) is a primary and / or secondary amine ketimine compound, an enamine compound, and / or
Or the high weather resistant matte sealing material composition according to any one of claims 1 to 5, which is an aldimine compound. 7. The highly weather-resistant matte sealing material composition according to claim 1, further comprising an average particle size of 1 or more.
A matt sealing material composition having high weather resistance and an uneven surface-forming surface, comprising a balloon having a size of 00 μm or more. 8. The balloon has an average particle size of 200 to 40.
The highly weather-resistant uneven surface-forming matting sealing material composition according to claim 7, which has a volume concentration of 0 to 25 μm and a volume concentration of the balloon in the sealing material composition of 10 to 25 vol%.