JP2013231154A - Primer composition for modified silicone-based sealing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a primer composition for a modified silicone-based sealing material, which has excellent adhesiveness to a poor-adhesive coated surface.SOLUTION: A primer composition for a modified silicone-based sealing material comprises a chlorinated polymer (A), a polyisocyanate compound (B), a silane coupling agent which has an epoxy group or an ureido group (C), a catalyst (D), and a solvent (E).

Description

  The present invention relates to a primer composition for a modified silicone sealant.

  Sealing materials are widely used in buildings and the like for filling joints and gaps between various members and ensuring watertightness and airtightness. Typical sealants for buildings include one-pack or two-pack sealants such as silicone sealants, modified silicone sealants, polyurethane sealants, and polysulfide sealants.

  Architectural sealing materials are required to exhibit adhesion to difficult-to-adhere coating surfaces such as acrylic electrodeposition coating surfaces and fluorine-based coating surfaces. A primer composition is used to improve the adhesion between the adherend and the sealing material (see, for example, Patent Documents 1 and 2).

  Patent Document 1 describes a primer composition that has good adhesion to polyolefin-based materials such as polyethylene and polypropylene, and also has good adhesion to modified silicone-based sealing materials.

  Patent Document 2 discloses a primer composition that can be used for various types of sealing materials and exhibits excellent adhesion to difficult-to-adhere construction members, particularly acrylic electrodeposition construction members. Have been described.

JP 2004-210894A JP 2002-309182 A

  However, in recent years, an aluminum sash for construction in high-rise buildings and the like has been subjected to super-weather-resistant acrylic electrodeposition coating with an emphasis on durability, and a primer composition with higher adhesion is required. .

  In addition, an aluminum sash coated with acrylic electrodeposition is often used in combination with various types of glass such as float glass, heat ray reflective glass, and heat ray absorbing glass, and a primer composition that adheres to any of these is required. .

  In addition, for adherends such as outer wall panels and headboards that have a hard-to-adhere coating surface and large thermal expansion and contraction, the sealing material peels off when the rubber elasticity of the sealing material is developed before the adhesion of the sealing material is developed. Since there exists a possibility, the primer composition with a quick initial adhesive expression is needed.

  In view of the above problems, an object of the present invention is to provide a primer composition for a modified silicone-based sealing material that has a fast initial appearance of adhesion and excellent adhesion to a difficult-to-adhere coating surface.

The present invention includes the following (1) to (6).
(1) a chlorinated polymer (A),
A polyisocyanate compound (B);
A silane coupling agent (C) having an epoxy group or a ureido group;
A catalyst (D);
Solvent (E),
A primer composition for a modified silicone-based sealant, comprising:
(2) Modified silicone type | system | group as described in said (1) whose content of the said silane coupling agent (C) is 5 to 100 mass parts with respect to 100 mass parts of said chlorinated polymers (A). Primer composition for sealing material.
(3) The primer composition for a modified silicone sealant according to (1) or (2), wherein the polyisocyanate compound (B) is a reaction product of an isocyanate compound and a diol having a number average molecular weight of 50 to 500. object.
(4) The primer composition for a modified silicone sealant according to any one of (1) to (3), wherein the catalyst (D) is one or both of a tin catalyst and an amine catalyst. .
(5) The modified silicone sealing material according to any one of (1) to (4), wherein the functional group bonded to silicon of the silane coupling agent (C) is a dimethoxy group or a trimethoxy group. Primer composition.
(6) The primer composition for a modified silicone-based sealing material according to any one of (1) to (5), which is used for adhesion between an acrylic electrodeposition coated surface or a fluorine-based painted surface and a sealing material.

  According to the present invention, it is possible to have excellent adhesion to a coating surface having a fast initial adhesion appearance and difficult adhesion.

FIG. 1 is a perspective view showing a state of a peel test.

  The present invention will be described in detail below. The present invention is not limited by the following modes for carrying out the invention (hereinafter referred to as embodiments). In addition, constituent elements in the following embodiments include those that can be easily assumed by those skilled in the art, those that are substantially the same, and those in a so-called equivalent range. Furthermore, the constituent elements disclosed in the following embodiments can be appropriately combined.

  The primer composition for a modified silicone sealant according to this embodiment (hereinafter referred to as “the composition of this embodiment”) includes a chlorinated polymer (A), a polyisocyanate compound (B), an epoxy group or A silane coupling agent (C) having a ureido group, a catalyst (D), and a solvent (E) are included.

<Chlorinated polymer (A)>
The chlorinated polymer (A) contained in the composition of the present embodiment is not particularly limited as long as it is a chlorinated polymer. Preferably, for example, a chlorinated product of isoprene-based synthetic rubber, chlorinated polyethylene, chlorine Chlorinated polypropylene, chlorinated polyethylene / propylene copolymer, chlorinated polybutadiene, chlorinated polystyrene, chlorinated polybutadiene / styrene copolymer, chlorosulfonated polyethylene, chlorosulfonated polyethylene / vinyl acetate copolymer, etc. The The chlorinated polymer (A) may be used in combination of two or more chlorinated polymers exemplified above.

  The chlorination rate of the chlorinated polymer (A) is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 70% by mass, and particularly preferably 40% by mass to 70% by mass. When the chlorination rate is 40% by mass or more and 70% by mass or less, excellent properties are exhibited in both adhesiveness and workability. The chlorination rate is a value measured by fluorescent X-ray analysis.

  The number average molecular weight (Mn) of the chlorinated polymer (A) is not particularly limited, but is preferably about 10,000 to 1,000,000. Particularly, if it is about 20,000 to 500,000, it has appropriate strength and stability. From the viewpoint of adhesion stability. Furthermore, the molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) is preferably as narrow as possible in that the viscosity at the same molecular weight is lowered.

<Polyisocyanate compound (B)>
The polyisocyanate compound (B) contained in the composition of the present embodiment is not particularly limited as long as it has two or more isocyanate groups in the molecule. The polyisocyanate compound (B) is preferably a reaction product of an isocyanate compound and a diol.

(Isocyanate compound)
Specific examples of the isocyanate compound (hereinafter referred to as “polyisocyanate compound”) include, for example, TDI (for example, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2). , 6-TDI)), MDI (for example, 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI)), 1,4-phenylene diisocyanate , Polymethylene polyphenylene polyisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate Aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI); transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), And alicyclic polyisocyanates such as bis (isocyanatemethyl) cyclohexane (H ₆ XDI) and dicyclohexylmethane diisocyanate (H ₁₂ MDI); these carbodiimide-modified polyisocyanates; these isocyanurate-modified polyisocyanates; and the like. Such polyisocyanate compounds can be used singly or in combination of two or more.

  In the present embodiment, it is preferable that the polyisocyanate compound has three or more isocyanate groups from the reason that the initial adhesiveness and the hot water resistant adhesiveness to the hardly-adhesive coated surface become better. Specific examples of the polyisocyanate compound having three or more isocyanate groups include tris (phenylisocyanate) thiophosphate, polymethylene polyphenylisocyanate, and a polyisocyanate compound having an isocyanurate ring. These may be used alone or in combination of two or more.

  Among these, it is preferable to use a combination of one or both of tris (phenylisocyanate) thiophosphate and polymethylene polyphenylisocyanate and a polyisocyanate compound having an isocyanurate ring. It is also preferable to use a combination of tris (phenylisocyanate) thiophosphate and a polyisocyanate compound having an isocyanurate ring. By using these in combination, it is possible to improve the initial adhesiveness and hot water-resistant adhesiveness to the difficult-to-adhere coating surface.

  As the polyisocyanate compound having an isocyanurate ring, an isocyanurate-modified product of a diisocyanate compound obtained by trimerizing a diisocyanate compound can be preferably used. Specific examples of the diisocyanate compound include the aromatic polyisocyanates exemplified above. Among these, the polyisocyanate compound having an isocyanurate ring obtained by reacting a mixture of TDI and HDI has better initial adhesiveness and hot water-resistant adhesiveness to difficult-to-adhere coating surfaces, and sufficient adhesion Is preferable because

  Examples of commercially available polyisocyanate compounds include polyisocyanate compounds having an isocyanurate ring (dismodule) obtained by reacting tris (phenylisocyanate) thiophosphate (Dismodule RFE, Bayer), a mixture of HDI and TDI. HL, manufactured by Bayer), polymethylene polyphenyl isocyanate (Sumijoule 44V-10, manufactured by Sumika Bayer Urethane Co., Ltd.) and the like can be suitably used.

(Diol)
The diol is not particularly limited as long as it is a compound having two or more hydroxyl groups (hereinafter referred to as “polyol compound”). Specifically, for example, ethylene glycol (EG), diethylene glycol, propylene glycol (PG), dipropylene glycol, butylene glycol, (1,3- or 1,4-) butanediol, (1,5-) pentanediol , Neopentyl glycol, (1,6-) hexanediol, cyclohexanedimethanol, glycerin, 1,2,5-hexanetriol, 1,1,1-trimethylolpropane (TMP), pentaerythritol, and other low molecular weight polyols; Saccharides such as sorbitol; polyether polyols such as polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyoxypropylene glycol, polyoxybutylene glycol; polybutadiene polyol, polyisopropyl Polyolefin polyols such as emissions polyol; adipate polyol; lactone polyol; and the like. Such polyol compounds can be used singly or in combination of two or more.

  Among these, butanediol, pentanediol, hexanediol, and the like are preferable because the initial adhesiveness and the hot water-resistant adhesiveness to the difficult-to-adhere coating surface are better.

  The number average molecular weight of the polyol compound (diol) is preferably 50 or more and 500 or less.

  The polyisocyanate compound (B) is obtained by reacting the above-described isocyanate compound with a diol (polyol compound).

  The polyisocyanate compound (B) is preferably a reaction product of an isocyanate compound and a diol having a number average molecular weight of 50 or more and 500 or less.

  The polyisocyanate compound (B) can be obtained by a known production method. The blending amount of the polyisocyanate compound and the diol (polyol compound) in producing the polyisocyanate compound (B) has an index (number of moles of isocyanate group / number of moles of hydroxy group) of 3 or more and 10 or less. preferable.

  The content of the polyisocyanate compound (B) is preferably 20 parts by mass or more and 500 parts by mass or less, and 50 parts by mass or more and 300 parts by mass with respect to 100 parts by mass of the chlorinated polymer (A) (binder resin). The following is more preferable, and 80 to 250 parts by mass is particularly preferable. When the content of the polyisocyanate compound (B) is within this range, the initial adhesiveness and the hot water-resistant adhesiveness to the difficult-to-adhere coating surface become better, and sufficient adhesiveness is obtained.

<Silane coupling agent (C)>
Examples of the silane coupling agent (C) contained in the composition of the present embodiment include an epoxy group, a ureido group (amino group), an amino group, a mercapto group, a (poly) sulfide group, a vinyl group, a methacryloxy group, and a carboxy group. And a silane coupling agent (C) having at least one organic functional group selected from the group consisting of a group, an isocyanate group, a halogen, and a cyclopropyl group. The silane coupling agent (C) contained in the composition of this embodiment preferably has an epoxy group or ureido group (amino group) in the molecule.

  Specifically, for example, γ-glycidoxypropyltrimethoxysilane represented by the following formula (1), γ-glycidoxypropylmethyldimethoxysilane represented by the following formula (2), and the following formula (3) Γ-glycidoxypropyl triethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane represented by the following formula (4), epoxy group-containing silane such as γ-glycidoxypropylmethyldiethoxysilane Compound;

  γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N- amino group-containing silane compounds such as β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; Ureido group-containing silane compounds such as γ-ureidopropyltrimethoxysilane represented by 5) and 3-ureidopropyltriethoxysilane represented by the following formula (6);

  Mercapto group-containing silane compounds such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane; bis (triethoxysilylpropyl) tetrasulfide, (Poly) sulfide group-containing silane compounds such as bis (triethoxysilylpropyl) disulfide; Vinyl group-containing silane compounds such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane; γ -Methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltri Methacryloxy group-containing silane compounds such as Tokishishiran;

  Carboxysilane compounds such as β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; Trimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatoethyltrimethoxysilane, γ-isocyanatoethyltriethoxysilane, γ-isocyanateethylmethyl Isocyanate group-containing silane compounds such as diethoxysilane and γ-isocyanatoethylmethyldimethoxysilane; N- (1,3-dimethylbutylidene) -3- (trimethoxy) Silyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (methyldimethoxy) Silyl) -1-propanamine, ketimine group-containing silane compounds such as N- (1,3-dimethylbutylidene) -3- (methyldiethoxysilyl) -1-propanamine; γ-chloropropyltrimethoxysilane and the like; Halogen-containing silane compounds; silyl esters such as methyl silyl esters; silane compounds such as orthosilicate esters and the like. These silane coupling agents may be used singly or in combination of two or more.

  Among the silane coupling agents (C), γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glycid represented by the above formulas (1) to (6). Xylpropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, and 3-ureidopropyltriethoxysilane improve adhesion to particularly difficult-to-adhere coating surfaces Preferred because of its excellent effect.

  In the composition of the present embodiment, an epoxy group-containing silane compound, a ureido group-containing silane compound, and an amino group-containing silane compound are suitably used in that they are excellent in adhesion to various difficult-to-adhere adhesive coating members. Among these, an epoxy group-containing silane compound or a ureido group-containing silane compound is more preferable. The epoxy group-containing silane compound is more preferably aliphatic than alicyclic.

  In addition, since the composition of the present embodiment includes the silane coupling agent (C) having an epoxy group or a ureido group, it is possible to promote the initial adhesion development to the hardly-adhesive coating surface. In addition, it is possible to improve the adhesiveness to adherends (for example, outer wall panels, headboards, etc.) having a difficult-to-adhere coating surface with large interlayer displacement. Thereby, even when the physical properties (rubber elasticity) of the sealing material are developed at an early stage, peeling of the sealing material can be suppressed.

  Moreover, since the reactivity becomes quicker than an ethoxy group when the functional group couple | bonded with the silicon of the said silane coupling agent (C) is a methoxy group, it has couple | bonded with the silicon of a silane coupling agent (C). The functional group is preferably a methoxy group rather than an ethoxy group.

  The functional group bonded to silicon of the silane coupling agent (C) is more preferably a dimethoxy group or a trimethoxy group. When the functional group is a methoxy group, the adhesion with the modified silicone sealant can be improved. In addition, when the functional group is a methoxy group, the initial adhesion development can be promoted, and therefore, the adhesiveness to the adherend of the difficult-to-adhesive painted surface having a large temperature displacement and interlayer displacement can be improved. Even when the physical properties (rubber elasticity) of the sealing material are developed, peeling of the sealing material can be suppressed.

  A commercial item may be used for the said silane coupling agent (C), and you may manufacture it. Manufacturing conditions are not particularly limited, and can be performed by known methods and conditions.

  The silane coupling agent (C) is preferably contained in an amount of 5 parts by mass to 100 parts by mass with respect to 100 parts by mass of the chlorinated polymer (A). If it is this range, the adhesiveness with respect to the hard-to-adhere coating surface of a primer composition can be improved, without having a bad influence on the physical property of hardened | cured material. Further, the content of the silane coupling agent (C) is preferably 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the chlorinated polymer (A), whereby the primer composition hardly adheres. It is possible to promote the initial adhesion development to the coated surface and to improve the initial heat-resistant adhesion.

  Since the composition of this embodiment contains the silane coupling agent (C) which has an epoxy group or a ureido group, such as a urethane type baking coating board, a fluorine-type coating board, an anodized aluminum board, an acrylic electrodeposition coating board, etc. It is possible to improve the adhesion to the hardly adhesive coated surface and the modified silicone sealant.

<Catalyst (D)>
The composition of this embodiment contains a catalyst (D). By containing the catalyst (D), the onset of adhesion is accelerated, and sufficient adhesion can be obtained even on difficult-to-adhere coating surfaces. The catalyst (D) contained in the composition of the present embodiment is not particularly limited as long as it can react with the curable resin. In the composition of the present embodiment, the catalyst (D) can be used as a curing agent for the chlorinated polymer (A).

  Examples of the catalyst (D) contained in the composition of the present embodiment include a metal catalyst, a tin catalyst, an amine catalyst, and the like in terms of excellent adhesion promoting effects.

  Examples of the metal catalyst, tin catalyst, and amine catalyst include organometallic compounds, tertiary amines, salts of tertiary amines and carboxylic acids, and the like. Specifically, examples of the organometallic compound include divalent tin compounds such as tin octoate, tin octylate, tin butanoate, tin naphthenate, tin caprylate and tin oleate; dibutyltin dioctoate, dibutyl Tin dilaurate, dibutyltin diacetate, dibutyltin dimaleate, dibutyltin distearate, dibutyltin dioleate, dioctyltin dilaurate, dioctyltin diversate, diphenyltin diacetate, dibutyltin dimethoxide, dibutyltin oxide, dibutyltin bis (triethoxysilicate), Tetravalent organotin compounds such as reaction products of dibutyltin oxide and phthalates; dibutyltin bis (acetylacetonate), tin-based chelate compounds, zirconium tetrakis (acetylacetonate), titanium tetrakis (acetate) Ruacetonate), aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), acetylacetone cobalt, acetylacetone iron, acetylacetone copper, acetylacetone magnesium, acetylacetone bismuth, acetylacetone nickel, acetylacetone zinc, acetylacetone manganese, and the like; Titanates such as tetra-n-butyl titanate and tetrapropyl titanate; and other metals other than tin such as manganese, iron, cobalt, copper, zinc, zirconium, lead, bismuth, such as lead octylate and zirconium octylate And metal organic acid salts with various organic acids such as octylic acid, stearic acid, and naphthenic acid. Examples of amines include primary amines such as butylamine, hexylamine, octylamine, dodecylamine, oleylamine, cyclohexylamine and benzylamine; secondary amines such as dibutylamine; diethylenetriamine, triethylenetetramine and guanidine. , Polyphenyls such as diphenylguanidine, xylylenediamine; triethylenediamine, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo [5,4,0] -7-undecene Cyclic amines; amino alcohol compounds such as monoethanolamine, diethanolamine and triethanolamine; amines such as aminophenol compounds such as 2,4,6-tris (dimethylaminomethyl) phenol Quaternary ammonium salts such as benzyltriethylammonium acetate; low molecular weight amide resin obtained from excess polyamine and polybasic acid; reaction product of excess polyamine and epoxy compound, etc. Is mentioned. In addition, triethylamine, tributylamine, triethylenediamine, hexamethylenetetramine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 1,4-diazabicyclo [2,2,2] octane (DABCO), Tertiary amines such as N-methylmorpholine and N-ethylmorpholine, or salts of these amines with carboxylic acid and the like. These catalysts can be used singly or in combination of two or more.

  Of these, tin-based catalysts and amine-based catalysts are preferred from the viewpoint of having a small amount and a large catalytic ability. Either one or both of the tin-based catalyst and the amine-based catalyst may be used. As the tin-based catalyst, either divalent or tetravalent may be used, or both may be used in combination. As the amine catalyst, tertiary amines are preferably used.

  In the present embodiment, by using the catalyst (D), the adhesion reaction speed with the sealing material can be increased, and the progress of the adhesion reaction can be promoted to shorten the working time for adhesion. The content of the catalyst (D) is preferably 0.01 parts by mass or more and 5 parts by mass or less, and more preferably 0.01 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the chlorinated polymer (A).

<Solvent (E)>
The composition of this embodiment contains a solvent (E). As the solvent (E), various conventionally known solvents are used as long as they are inert to the chlorinated polymer (A), the polyisocyanate compound (B), the silane coupling agent (C) and the catalyst (D). be able to. There is no restriction | limiting in particular as a solvent (E), A well-known thing, such as an organic solvent and a water-soluble solvent, can be used. Specifically, for example, hydrocarbons such as benzene, toluene, xylene, hexane, heptane, octane and cyclohexane; halogenated hydrocarbons such as tetrachloromethane and methylene chloride; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone type; ether type such as diethyl ether, tetrahydrofuran, dioxane, etc .; ester type such as methyl acetate, ethyl acetate, butyl acetate; ether ester type such as cellosolve acetate, butylcellosolve acetate; methanol, ethanol, propanol, i-propanol, n -Alcohols such as butanol; petroleums ranging from gasoline such as mineral spirits to kerosene fractions; N-methyl-2-pyrrolidone, N, N-dimethylformamide, dimethylacetate Amide. These solvents may be used alone or in combination of two or more.

  Of these, methyl ethyl ketone and ethyl acetate are preferable because the adhesion rate is improved. The solvent is preferably used after sufficiently dried or dehydrated. The content of the solvent (E) in the composition of the present embodiment can be appropriately changed according to the use, purpose, etc. of the composition.

  It is preferable that content of the said solvent (E) is 60 to 95 mass% of the total mass (total mass) of the composition of this embodiment. If content of a solvent (E) is this range, favorable applicability | paintability can be obtained.

  Moreover, the composition of this embodiment can contain various additives as needed in addition to the components described above as long as the object of the present invention is not impaired. Examples of the additive include pigments, dyes, antioxidants, antioxidants, antistatic agents, flame retardants, adhesion promoters, stabilizers, dispersants, fillers, and the like.

  The pigment may be either an inorganic pigment or an organic pigment. For example, an organic pigment such as titanium oxide, zinc oxide, ultramarine, red, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate inorganic pigment, azo pigment, copper phthalocyanine pigment, and the like can be used.

  The dye is not particularly limited, and conventionally known dyes can be used. For example, when the resin molded product is black, black dye, yellow dye, red dye, blue dye, and brown dye can be used.

  Examples of the anti-aging agent include hindered phenol compounds and hindered amine compounds.

  Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).

  Examples of the antistatic agent include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

  Examples of the flame retardant include chloroalkyl phosphate, dimethyl / methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, and brominated polyether.

  Examples of the adhesion imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins, and epoxy resins.

  Examples of the stabilizer include fatty acid silyl esters and fatty acid amide trimethylsilyl compounds.

  The dispersant refers to a substance that makes a solid into fine particles and disperses it in a liquid, and examples thereof include sodium hexametaphosphate, sodium condensed naphthalenesulfonate, and a surfactant.

  Examples of the filler include organic or inorganic fillers having various shapes. Specifically, for example, fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; calcium carbonate, magnesium carbonate, zinc carbonate; Examples thereof include wax stone clay, kaolin clay, calcined clay; organic or inorganic fillers such as carbon black; treated products of these fatty acids, treated resin acids, treated urethane compounds, treated fatty acid esters; and the like.

  The various additives described above can be used in appropriate combination.

  The method for producing the composition of the present embodiment is not particularly limited. For example, each of the above components may be used under a reduced pressure or an inert gas atmosphere such as nitrogen using a stirring device such as a ball mill, a universal agitator, or a mixing mixer. Examples of the method include mixing by sufficiently kneading and uniformly dispersing.

  Thus, the composition of this embodiment comprises a chlorinated polymer (A), a polyisocyanate compound (B), a silane coupling agent (C) having an epoxy group or a ureido group, and a catalyst (D). And a solvent (E). A primer composition for a modified silicone sealant. Therefore, it is possible to improve the initial adhesiveness, the hot water resistant adhesiveness and the initial heat resistant adhesiveness with respect to the coated surface having poor adhesion or adhesiveness with the modified silicone sealant. Moreover, by including the silane coupling agent (C) which has an epoxy group or a ureido group, initial adhesion expression can be accelerated | stimulated and the adhesiveness with respect to a difficult-to-adhere coating surface can be improved. Therefore, it can have excellent adhesion to a difficult-to-adhere coating surface.

  The use of the composition of the present embodiment is not particularly limited, but the composition of the present embodiment has the excellent characteristics as described above. Therefore, it is used for construction, civil engineering, concrete, wood, metal, glass. It is suitably used for applications such as sealing materials for plastics and plastics. Especially, since the composition of this embodiment can accelerate | stimulate initial stage | formula adhesion | attachment, for example, the adherend (for example, outer wall panel, head board etc.) of the hard-to-adhesive coating surface with a large temperature displacement and interlayer displacement is large. Can be suitably used.

  Moreover, the composition of this embodiment can be used suitably also as a primer for a hardly-adhesive coating member. Examples of the material of the hardly-adhesive coating member that can suitably use the composition of the present embodiment include acrylic electrodeposition coating and fluorine baking coating. These hard-to-adhere members are used in, for example, automobiles, vehicles, buildings, electronic parts, and the like. Moreover, the composition of this embodiment can be used also for members other than a hard-to-adhere coating member.

  The method for adhering the composition of the present embodiment to a hardly adhesive coating member is not particularly limited. For example, the composition of the present embodiment can be applied and immersed in a difficult-to-adhere coating member to be adhered. The composition of the present embodiment is preferably cured under conditions of 5 ° C. or higher and 40 ° C. or lower and 30% RH or higher and 70% RH or lower.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
<Preparation of polyisocyanate compound (B)>
Each component shown in Table 1 is blended in the blending amounts (parts by mass) shown in the same table, and these are uniformly mixed and reacted under conditions of a reaction temperature of 40 ° C. or higher and 150 ° C. or lower. A polyisocyanate compound (B) was prepared. Table 1 shows the amount of each component. Also, in a solvent (for example, ethyl acetate), an isocyanate compound and a diol are mixed in such an amount that the isocyanate group is excessive with respect to the hydroxyl group of the polyol, and if necessary, a catalyst is used and the temperature is 40 ° C. or higher. A polyisocyanate compound (B) can also be obtained by reacting under conditions of 150 ° C. or lower.

Each component shown in Table 1 is as follows.
・ Isocyanate compound: Dismodule HL, manufactured by Bayer ・ Diol: 1,4-butanediol

<Preparation of primer composition>
Each component shown in Table 2 was blended in the blending amount (parts by mass) shown in the same table, and these were uniformly mixed to prepare each primer composition shown in Table 2. Table 2 shows the amount of each component in each example and comparative example.

<Peel test (peel test)>
FIG. 1 is a perspective view showing a state of a peel test. Each primer composition 11 obtained was applied to a melamine resin-coated super-weather-resistant acrylic electrodeposition coating plate 12 and allowed to stand at 20 ° C. for 2 minutes, and then a modified silicone-based sealant 13 (trade name: Super II, Yokohama) Rubber Co., Ltd.) was applied and cured under the following curing and curing conditions to obtain a test specimen.
(Curing and curing conditions)
-Initial adhesiveness: left at 20 ° C for 3 days, then left at 50 ° C for 4 days-Hot water resistant adhesion: left at 20 ° C for 3 days, then left at 50 ° C for 4 days, and further in warm water at 50 ° C 7 days immersion

About each obtained test body, the 90 degree peeling test (peel test) of each primer composition 11 was done by the method shown below, and the destruction state was evaluated. As shown in FIG. 1, the sealing material 13 was peeled from the adherend 12 in the direction of arrow A so as to be 90 degrees with respect to the adherend 12. The results are shown in Table 2. In Table 2, the evaluation criteria for CF and AF are as follows.
(Evaluation criteria)
-CF: The material that resulted in cohesive failure of the sealing material-AF: The material peeled off at the interface between the sealing material and the primer composition It was evaluated that CF was superior in adhesiveness.

Each component shown in Table 2 is as follows.
Chlorinated polymer (A): Pergut S170, manufactured by Sumika Bayer Co., Ltd. Polyisocyanate compound (B): compound obtained by preparing in Table 1 above Catalyst (D): stannous octylate, stannoct・ Number average molecular weight 405, manufactured by API Corporation ・ Solvent (E): Ethyl acetate, manufactured by Kanto Chemical Co., Ltd. ・ Silane coupling agent (C) 1: 3-glycidoxypropyltrimethoxysilane, number average molecular weight 236.3, KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd. ・ Silane coupling agent (C) 2: 3-glycidoxypropylmethyldimethoxysilane, number average molecular weight 220.3, KBM-402, Shin-Etsu Chemical Co., Ltd. -Silane coupling agent (C) 3: 3-glycidoxypropyltriethoxysilane, number average molecular weight 278.4, KB -403, manufactured by Shin-Etsu Chemical Co., Ltd. Silane coupling agent (C) 4: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, number average molecular weight 246.4, KBM-303, Shin-Etsu Chemical Co., Ltd. -Silane coupling agent (C) 5: 3-ureidopropyltriethoxysilane, number average molecular weight 264.4, KBE-585, manufactured by Shin-Etsu Chemical Co., Ltd.-Silane coupling agent (C) 6: 3-methacryloxy Propyltrimethoxysilane, number average molecular weight 248.4, KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd. Silane coupling agent (C) 7: 3-acryloxypropyltrimethoxysilane, number average molecular weight 234.3, KBM- 5103, manufactured by Shin-Etsu Chemical Co., Ltd. ・ Silane coupling agent (C) 8: anilinotriethoxysilane Number average molecular weight 255.4, Y9669, manufactured by Nihon Unicar Co., Ltd. ・ Silane coupling agent (C) 9: Ketimine triethoxysilane, number average molecular weight 221.4, S340, manufactured by Chisso Corporation ・ Silane coupling agent (C ) 10: 3-isocyanatopropyltriethoxysilane, number average molecular weight 247.4, KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd. ・ Silane coupling agent (C) 11: aminopropyltriethoxysilane, number average molecular weight 425.7 A1170, manufactured by Nihon Unicar Co., Ltd. ・ Silane coupling agent (C) 12: 3-aminopropyldiethoxysilane, number average molecular weight 221.4, KBM-902, manufactured by Shin-Etsu Chemical Co., Ltd.

  From the results shown in Table 2, in Examples 1 to 6, 9, and 10, the fracture mode is CF (cohesive fracture) for both initial adhesiveness and hot water resistant adhesiveness. It was confirmed that it was excellent in performance. In Examples 7 and 8, it was confirmed that the fracture mode was excellent in initial adhesiveness because the initial adhesiveness was CF and the hot water resistant adhesiveness was AF (interfacial peeling).

  On the other hand, in Comparative Examples 1 to 5 and 7, the fracture mode is interfacial debonding (AF) between the sealing material 13 and the primer composition 11 for both the initial adhesiveness and the hot water resistant adhesiveness. These were confirmed to be inferior in initial adhesiveness and hot water resistant adhesiveness. In Comparative Examples 6 and 8, the fracture mode was CF for the initial adhesiveness and AF for the hot water resistant adhesiveness, and it was confirmed that the initial adhesiveness was excellent but the hot water resistant adhesive property was poor.

  As for the silane coupling agent (C) which has an epoxy group, it was confirmed that an aliphatic type is better in hot water-resistant adhesiveness than an alicyclic type (see Examples 1 to 6 and 8). It was confirmed that the functional group bonded to silicon of the silane coupling agent (C) is a dimethoxy group or a trimethoxy group, which has better hot water adhesion than the triethoxy group (Examples 1 to 6, 7).

  Therefore, the primer composition in which the functional group bonded to silicon of the silane coupling agent (C) having an epoxy group or a ureido group is a dimethoxy group or a trimethoxy group is more difficult to adhere than a conventional primer composition. Therefore, it can be suitably used as a primer composition for difficult-to-adhere adhesive surfaces and modified silicone sealants.

<Preparation of primer composition>
Each component shown in Table 3 was blended in the blending amount (parts by mass) shown in the same table, and these were uniformly mixed to prepare each primer composition shown in Table 3. Table 3 shows the amount of each component in each example and comparative example.

<Peel test (peel test)>
FIG. 1 is a perspective view showing a state of a peel test. Each primer composition 11 thus obtained was applied to a fluorine-based coating plate 12 and a melamine resin-coated super-weather-resistant acrylic electrodeposition coating plate 12 and allowed to stand at 20 ° C. for 2 minutes, and then a modified silicone-based sealing material 13 (product) Name: Super II, manufactured by Yokohama Rubber Co., Ltd.) was applied and cured under the following curing and curing conditions to obtain a test specimen.
[Hardening and curing conditions]
-Initial heat resistant adhesion: left at 40 ° C for 1 day, and left at 23 ° C for 3 days-Initial adhesiveness: left at 20 ° C for 3 days, then left at 50 ° C for 4 days-Hot water resistant adhesion: 3 at 20 ° C After being left for a day, left at 50 ° C for 4 days and then immersed in warm water at 50 ° C for 7 days

About each obtained test body, the 90 degree peeling test (peel test) of each primer composition 11 was done by the method shown below, and the destruction state was evaluated. As shown in FIG. 1, the sealing material 13 was peeled from the adherend 12 in the direction of arrow A so as to be 90 degrees with respect to the adherend 12. In addition, about initial heat-resistant adhesiveness, the 90 degree peeling test (peel test) was done on the conditions of 60 degreeC and 80 degreeC. The results are shown in Table 3. In Table 3, the evaluation criteria for CF and AF are as follows.
[Evaluation criteria]
(Initial heat resistant adhesiveness)
-CF: what resulted in cohesive failure of the sealing material-AF: area ratio of interfacial peeling between the sealing material and the primer composition.
(Initial adhesiveness, hot water resistant adhesiveness)
-CF: The material that resulted in cohesive failure of the sealing material-AF: The material peeled off at the interface between the sealing material and the primer composition It was evaluated that CF was superior in adhesiveness.

Each component shown in Table 3 is as follows.
Chlorinated polymer (A): Pergut S170, manufactured by Sumika Bayer Co., Ltd. Polyisocyanate compound (B): compound obtained by preparing in Table 1 above Catalyst (D): stannous octylate, stannoct・ Number average molecular weight 405, manufactured by API Corporation ・ Solvent (E): Ethyl acetate, manufactured by Kanto Chemical Co., Ltd. ・ Silane coupling agent (C) 13: 3-glycidoxypropyltrimethoxysilane, number average molecular weight 236.3, KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd. ・ Silane coupling agent (C) 14: 3-glycidoxypropylmethyldimethoxysilane, number average molecular weight 220.3, KBM-402, Shin-Etsu Chemical Co., Ltd. -Silane coupling agent (C) 15: 3-glycidoxypropyltriethoxysilane, number average molecular weight 278.4 KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd. ・ Silane coupling agent (C) 16: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, number average molecular weight 246.4, KBM-303, Shin-Etsu Chemical Co., Ltd. -Silane coupling agent (C) 17: Vinyltrimethoxysilane, number average molecular weight 148.2, KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.-Silane coupling agent (C) 18: 3-isocyanatopropyltriethoxy Silane, number average molecular weight 247.4, KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd. ・ Silane coupling agent (C) 19: Anilinotriethoxysilane, number average molecular weight 255.4, Y9669, manufactured by Nihon Unicar Co., Ltd. Coupling agent (C) 20: aminopropyltriethoxysilane, number average Molecular weight 425.7, A1170, manufactured by Nihon Unicar Co., Ltd. ・ Silane coupling agent (C) 21: 3-aminopropyldiethoxysilane, number average molecular weight 221.4, KBM-902, manufactured by Shin-Etsu Chemical Co., Ltd.

  From the results shown in Table 3, in Examples 11 to 17, since the fracture forms are both initial heat resistant adhesiveness (60 ° C. and 80 ° C.) of CF (cohesive fracture) and AF (interfacial peeling) 20 or less, It was confirmed that it was excellent in heat-resistant adhesion. In Examples 11 to 15, since both initial adhesiveness and hot water resistant adhesiveness were CF, it was confirmed that both were excellent in initial adhesiveness and hot water resistant adhesiveness. In Examples 16 and 17, since the initial adhesiveness was CF and the hot water resistant adhesiveness was AF, the fracture form was confirmed to be excellent in initial adhesiveness.

  On the other hand, in Comparative Examples 9 to 14, since the fracture forms were both initial heat resistant adhesiveness (60 ° C. and 80 ° C.) AF20 or higher, it was confirmed that the initial heat resistant adhesiveness was inferior. In Comparative Examples 9, 10, 12, and 13, since both of the initial adhesiveness and the hot water resistant adhesiveness were AF, it was confirmed that all were inferior in the initial adhesiveness and hot water resistant adhesiveness. In Comparative Examples 11 and 14, since the initial adhesiveness was CF and the hot water adhesive property was AF, the fracture mode was confirmed to be excellent in initial adhesive property but poor in hot water adhesive property.

  The primer composition containing a predetermined amount of the silane coupling agent (C) having an epoxy group was confirmed to have good initial heat-resistant adhesion (60 ° C. and 80 ° C.) (see Examples 11 to 17). It was confirmed that the functional group bonded to silicon of the silane coupling agent (C) was better in initial heat-resistant adhesion than the triethoxy group when the dimethoxy group or the trimethoxy group was used (see Examples 11 to 17). ).

  Therefore, the primer composition containing a predetermined amount of the silane coupling agent (C) having an epoxy group and the functional group bonded to silicon of the silane coupling agent (C) is a dimethoxy group or a trimethoxy group, Compared to conventional primer compositions, it can improve the initial adhesion to difficult-to-adhere coating surfaces and is excellent in initial heat-resistant adhesive, initial adhesiveness and hot water-resistant adhesive properties. It can be suitably used as a primer composition for modified silicone sealants.

11 Primer composition 12 Substrate 13 Sealing material

Claims (6)

A chlorinated polymer (A);
A polyisocyanate compound (B);
A silane coupling agent (C) having an epoxy group or a ureido group;
A catalyst (D);
Solvent (E),
A primer composition for a modified silicone-based sealant, comprising:   The primer for a modified silicone sealant according to claim 1, wherein the content of the silane coupling agent (C) is 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the chlorinated polymer (A). Composition.   The primer composition for a modified silicone sealant according to claim 1 or 2, wherein the polyisocyanate compound (B) is a reaction product of an isocyanate compound and a diol having a number average molecular weight of 50 or more and 500 or less.   The primer composition for a modified silicone sealant according to any one of claims 1 to 3, wherein the catalyst (D) is one or both of a tin catalyst and an amine catalyst.   The primer composition for a modified silicone sealant according to any one of claims 1 to 4, wherein the functional group bonded to silicon of the silane coupling agent (C) is a dimethoxy group or a trimethoxy group.   The primer composition for a modified silicone sealant according to any one of claims 1 to 5, which is used for adhesion between an acrylic electrodeposition coated surface or a fluorine-based painted surface and a sealant.

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