JP2002265868A - Primer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a primer composition having excellent adhesion to a porous base material such as a concrete, a mortar or a polyvinyl chloride(PVC) coated steel plate and having excellent storing stability. SOLUTION: This primer composition is characterized by comprising (A) 2-80 wt.% of a compound which is a reactional product of an aminosilane and two kinds of epoxysilanes having different hydrolysis rates and has a hydrolyzable silyl group, (B) 0.1-10 wt.% of an organotitanium compound and/or a condensate thereof, (C) 2-30 wt.% of a film forming resin and (D) >=5 wt.% of a volatile solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a primer composition, and more particularly, to a primer composition having excellent adhesion to a porous substrate such as concrete, mortar, or PVC steel plate, and having excellent storage stability. .

[0002]

2. Description of the Related Art Conventionally, a urethane sealant has been used for bonding an automobile body to a windshield. Since a certain kind of urethane sealant has poor adhesiveness to glass, a primer is usually applied to the glass surface. ing. As a primer for the above application,
No. 5,110,054 discloses a primer composition comprising a film-forming resin, a reactant obtained by reacting a predetermined amount of aminosilane and epoxysilane in two steps, and a volatile solvent. This primer composition shows an excellent effect of improving adhesiveness by compounding a reactant obtained by reacting aminosilane and epoxysilane in two steps, and application to other uses as a primer will be studied. Have been. However, this primer has high adhesion to non-porous substrates such as glass,
Adhesion to a porous substrate such as concrete, mortar or PVC steel plate was insufficient. Improvements in storage stability have also been desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a primer composition which has excellent adhesion to a porous substrate such as concrete, mortar or PVC steel sheet and has excellent storage stability. I do.

[0004]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, they have used two kinds of compounds having different hydrolyzabilities as epoxysilane to be reacted with aminosilane, By adding a compound and / or a condensate thereof, it was found that the adhesion to a porous substrate was improved and the balance with storage stability was excellent, and the present invention was completed.

That is, the present invention relates to a compound 2 having a hydrolyzable silyl group, which is a reaction product of (A) an aminosilane and two types of epoxysilanes having different hydrolysis rates.
To 80% by weight, (B) 0.1 to 10% by weight of an organic titanium compound and / or a condensate thereof, (C) 2 to 30% by weight of a film-forming resin, and (D) 5% by weight or more of a volatile solvent. And a primer composition comprising:

Here, the organic group of the (B) organotitanium compound is preferably selected from the group consisting of acetylacetone residues, acetoacetic ester residues, glycol residues, alcohol residues and carboxylic acid residues.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The primer composition of the present invention (hereinafter, also referred to as “the composition of the present invention”) is a reaction product of (A) aminosilane and two kinds of epoxysilanes having different hydrolysis rates. A hydrolyzable silyl group-containing compound, (B) an organic titanium compound and / or a condensate thereof, (C) a film-forming resin, and (D) a volatile solvent in a predetermined quantitative ratio. It is characterized by: Less than,
Each component will be described in detail.

(A) Compound having a hydrolyzable silyl group The compound having a hydrolyzable silyl group of the present invention has at least one compound in a molecule formed from an aminosilane and two types of epoxysilanes having different hydrolysis rates. It is a compound having one hydrolyzable silyl group (hereinafter, also referred to as “silane compound”).

Here, the term "hydrolyzable silyl group" means a silyl group substituted with at least one alkoxyl group. The alkoxyl group is not particularly limited as long as it has a linear or branched alkyl group having 1 to 18 carbon atoms, and preferably includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like. Preferred examples of the hydrolyzable silyl group include a trimethoxysilyl group, a triethoxysilyl group, a methyldiethoxysilyl group, a methyldimethoxysilyl group, a dimethylethoxysilyl group, and a dimethylmethoxysilyl group.

The aminosilane used in the present invention is a compound having at least one amino group and at least one hydrolyzable silyl group in a molecule. Examples of the aminosilane having one amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-aminopropylmethyldiethoxysilane. Examples of the aminosilane having two amino groups include N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, and N- (β-amino Ethyl) -γ-aminomethyltrimethoxysilane, N
-(Β-aminoethyl) -γ-aminopropyltriethoxysilane and the like.

Among them, aminosilanes having two amino groups are preferred from the viewpoint of a high hydrolysis rate and excellent adhesiveness. Among them, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane and N- ( β-aminoethyl)
-Γ-aminopropylmethyldimethoxysilane, N-
(Β-aminoethyl) -γ-aminomethyltrimethoxysilane is preferred.

The epoxy silane used in the present invention is a compound having at least one glycidoxy group and at least one hydrolyzable silyl group in a molecule.
As the epoxy silane, preferably, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ -Glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyltrimethoxysilane, β- (3
4-epoxycyclohexyl) ethylmethyldimethoxysilane and the like.

In the present invention, two of these epoxy silanes having different hydrolysis rates are used in combination. Epoxysilanes can be used in combination of any two as long as they have different hydrolysis rates. This is because the use of two types having different hydrolysis rates provides an excellent balance between adhesion and storage stability.

Epoxysilanes having different hydrolysis rates are:
For example, a combination in which the number of alkoxyl groups of the hydrolyzable silyl group is different, a combination in which the chain length of the alkoxyl group is different, and a combination of both are different.

Among them, in the present invention, it is preferable to use bifunctional and trifunctional epoxysilanes in combination. Specifically, γ
-Glycidoxypropylmethyldimethoxysilane, γ-
At least one selected from glycidoxypropylmethyldiethoxysilane and β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, and γ-
Glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, and β- (3,4-
It is preferable to combine with at least one selected from epoxycyclohexyl) ethylmethyltrimethoxysilane. Particularly preferred is a combination of γ-glycidoxypropylmethyldimethoxysilane and γ-glycidoxypropyltrimethoxysilane.

The mixing ratio (molar ratio) is, for example, when bifunctional and trifunctional epoxysilanes are used, bifunctional epoxysilane / 3-functional epoxysilane = 3/7 to 9/1
Is preferred, and 3/7 to 8/2 is more preferred. The reason for this is that when used in this range, the balance between adhesion and storage stability is particularly excellent.

The reaction ratio (molar ratio) between aminosilane and epoxysilane is aminosilane / epoxysilane = 1/2.
１ ／ to 好 ま し く is preferred, and ２〜 to 1 / 2.8 is more preferred.

The method for synthesizing the silane compound of the present invention is not particularly limited. For example, in the presence or absence of a solvent, aminosilane and two kinds of epoxysilane are mixed, and
It is obtained by heating to 60 ° C. and reacting for 20 to 50 hours.
When a solvent is used, it is preferable to use a solvent having an appropriate volatility such as methyl ethyl ketone or ethyl acetate, and it is preferable that the amount of the solvent used is 80% by weight or less of the reaction mixture.
When a solvent is used in the above reaction, the solvent may be removed and then added to the composition, or the solvent may be added without removing the solvent.

The compounding amount of the silane compound in the composition of the present invention is 2 to 80% by weight, preferably 3 to 70% by weight,
More preferably, it is 5 to 50% by weight. If the amount is less than 2% by weight, the adhesiveness is not sufficient, and if it exceeds 80% by weight, the storage stability decreases.

(B) Organotitanium compound and / or condensate thereof The organotitanium compound used in the composition of the present invention is not particularly limited as long as it has a structure represented by the following formula (1). Can be used.

[0021]

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Here, R represents an organic group and each independently represents an acetylacetone residue, an acetoacetate residue,
It is preferably a group selected from the group consisting of a glycol residue, an alcohol residue and a carboxylic acid residue.

The acetylacetone residue used in the present invention is represented by the following formula. (However, in the following formula, M represents a metal.)

[0024]

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The acetoacetic ester residue used in the present invention is represented by the following formula.

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R ¹ in the formula is a linear or branched alkyl group having 1 to 18 carbon atoms, and specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
Pentyl, isopentyl, neopentyl, hexyl, 2
-A group consisting of ethylhexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, or a combination thereof. Among them, methyl and ethyl are easily available industrially.

Further, the glycol residue used in the present invention is represented by the following formula.

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R ² in the formula is a linear or branched alkylene group having 2 to 18 carbon atoms, specifically, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, Examples include octamethylene, nonamethylene, decamethylene, octadecamethylene, 1-propyl-2-ethylpropylene, and a group composed of a combination thereof. Among these, those of 1-propyl-2-ethylpropylene are easily available industrially.

The alcohol residue used in the present invention is represented by the following formula.

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R ³ in the formula is a linear or branched alkyl group having 1 to 18 carbon atoms, and specific examples thereof include the same as those exemplified for R ¹ . Among them, n-propyl, isopropyl, butyl, octyl, 2-ethylhexyl, octadecyl and the like are preferable.

The carboxylic acid residue used in the present invention is represented by the following formula.

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R ⁴ in the formula is a linear or branched alkyl group having 1 to 18 carbon atoms, and specific examples thereof include the same as those exemplified for R ¹ . Among them, pentadecyl, heptadecyl and the like are preferable.

The organotitanium compound represented by the formula (1) of the present invention may have, as R, one of these residues alone or in combination of two or more. Above all, it is preferable that at least one of R is a group selected from the group consisting of an acetylacetone residue, an acetoacetate ester residue, and a glycol residue, since storage stability is particularly excellent.

Preferred examples of the organic titanium compound of the present invention include compounds represented by the following formulas (a) to (e).

[0035]

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Further, in the organotitanium compound of the present invention, the alkoxyl group contained in the residue R may be easily hydrolyzed by the presence of water to cause a condensation reaction between molecules. The composition of the present invention contains the condensate thus produced together with the above-mentioned organotitanium compound or alone, and when having two or more glycol residues as R, the composition is subjected to an intramolecular condensation reaction. It may contain the condensate formed.

As the organic titanium compound and / or condensate thereof of the present invention, more specifically, tetra-n-butoxytitanium, tetramer of tetra-n-butoxytitanium,
Titanium tetraacetylacetonate, diisopropoxybis (ethylacetoacetate) titanium, di (2-ethylhexoxy) bis (2-ethyl-1,3-hexanediolato) titanium, tetrastearyloxytitanium, and the like are preferred.

The compounding amount of the organic titanium compound and / or its condensate in the composition of the present invention is 0.1 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.1 to 2% by weight. %. If the content is less than 0.1% by weight, sufficient adhesiveness cannot be obtained, and if it exceeds 10% by weight, the viscosity increases and the storage stability decreases.

(C) Film-forming resin The film-forming resin used in the present invention is not particularly limited as long as it has a film-forming property, and known resins can be used. As film-forming resins, polycarbonates,
Polyesters, polyamides, polyurethanes, polystyrenes, polyarylethers, polyarylsulfones, polybutadienes, polysulfones, polyethersulfones, polyethylenes, polypropylenes, polyimides, polymethylpentenes, polyphenylene sulfides , Polyvinyl acetic acid, polysiloxanes, polyvinyl acetal, polyamides, polyimides, acrylic resin, amino resin, phenylene oxide resin, terephthalic acid resin, phenoxy resin, epoxy resin, phenolic resin, polystyrene-acrylonitrile copolymer, poly Vinyl chloride, vinyl chloride-vinyl acetate copolymer, acrylate copolymer, alkyd resin, cellulose film former, poly (amide imide), styrene-butadiene Polymer, vinylidene chloride-vinyl chloride copolymer, vinyl acetate-vinylidene chloride copolymer, ethylene-vinyl acetate copolymer, styrene-alkyd resin, polyvinyl carbazole, chlorinated polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene And aromatic terpene resins. These polymers are block, random or alternating copolymers. These may be used alone or in combination of two or more.

Among them, it is preferable to include an acrylic resin and an epoxy resin. This is because it has excellent weather resistance and curability. The amount ratio (weight ratio) of acrylic resin and epoxy resin is
Acrylic resin / epoxy resin is preferably 0.1 to 5,
0.3 to 4 is more preferable, and 0.7 to 3.5 is particularly preferable.

In the present invention, it is preferable to use one or more aromatic terpene resins, chlorinated polypropylenes or chlorinated polyethylenes in addition to the acrylic resin and the epoxy resin, thereby improving the adhesiveness to the porous material.

The aromatic terpene resin, chlorinated polypropylene, chlorinated polyethylene or a mixture thereof is preferably 5 to 95% by weight, more preferably 10 to 80% by weight, and more preferably 15 to 70% by weight, based on the total amount of the acrylic resin and the epoxy resin.
% By weight is particularly preferred.

As the acrylic resin used in the present invention, a known polymer or copolymer of an acrylic ester or a methacrylic ester can be used. Among them, copolymers composed of two kinds of methacrylic esters having different chain lengths of alkyl groups are preferable, and particularly, methacrylic esters having an alkyl group having 1 to 2 carbon atoms and methacryl having an alkyl group having 4 to 10 carbon atoms are preferable. It is preferably a copolymer with an acid ester. This is because the adhesiveness and storage stability are well balanced.

Examples of the methacrylate (a) having an alkyl group having 1 to 2 carbon atoms include methyl methacrylate (MMA) and ethyl methacrylate, with methyl methacrylate being particularly preferred.

Examples of the methacrylate (b) having an alkyl group having 4 to 10 carbon atoms include n-butyl methacrylate (BMA), isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, and cyclohexyl methacrylate. And benzyl methacrylate, etc., with n-butyl methacrylate and isobutyl methacrylate being particularly preferred.

The amount ratio (weight ratio) of the methacrylate (a) and the methacrylate (b) is such that (a) / (b) = 9 because the balance between adhesion and storage stability is particularly excellent.
0/10 to 30/70 is preferable, and 70/30 to 40 /
60 is more preferred.

Further, in addition to the above two methacrylic esters, a monomer (c) containing a hydroxyl group, an alkoxysilyl group or the like can be copolymerized. By introducing the above functional group into the side chain of the copolymer, the adhesiveness is further improved. The monomer (c) is preferably used in an amount of 1 to 50% by weight based on the total of (a) and (b).
-30% by weight is more preferred.

As the monomer (c), methacrylic acid 2-
Hydroxyethyl (HEMA), 2-hydroxypropyl methacrylate, 2-hydroxy-3-phenyloxypropyl acrylate, vinyltrimethoxysilane, vinyltriethoxysilane, tris- (2-methoxyethoxy) vinylsilane, γ- (methacryloxy Propyl) trimethoxysilane and the like. These monomers may be used alone or in combination of two or more. Among them, HEMA, 2-hydroxy-3-acrylate, in terms of adhesiveness
Phenyloxypropyl and γ- (methacryloxypropyl) trimethoxysilane are preferred.

In addition, other vinyl monomers and radical monomers may be copolymerized as long as the object of the present invention is not impaired.

The method for producing the acrylic resin is not particularly limited, and may be a known method. For example, in a volatile solvent such as methyl ethyl ketone or ethyl acetate, polymerization initiation of the methacrylic acid ester (a), (b), (c), another monomer as necessary, and a peroxide or an azo compound is performed. A method in which an agent is added and reacted at 50 to 90 ° C. for 6 to 48 hours for radical polymerization. When a solvent is used in the above reaction, the solvent may be removed and then added to the composition, or the solvent may be added without removing the solvent.

The epoxy resin used in the present invention is not particularly limited, and a known epoxy resin can be used. As the epoxy resin, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, novolak epoxy resin, epoxy resin having a fluorene skeleton, phenol compound and Epoxy resin, diglycidyl resorcinol, tetrakis (glycidyloxyphenyl) ethane, tris (glycidyloxyphenyl) methane, trisglycidylaminophenol, triglycidylaminocresol, tetraglycidylxylenediamine, etc. made from a copolymer of dicyclopentadiene as a raw material Alicyclic epoxy resins such as glycidylamine type epoxy resin and vinylcyclohexene diepoxide; and these may be used alone or in combination of two or more. Rukoto can also.

Of these, bisphenol A type epoxy resin is preferred because of its particularly excellent adhesiveness.

The amount of the film-forming resin in the composition of the present invention is 2 to 30% by weight, preferably 3 to 25% by weight, more preferably 5 to 20% by weight. If it is less than 2% by weight, the curability is not sufficient, and if it exceeds 30% by weight, the viscosity increases and the storage stability decreases.

(D) Volatile Solvent The primer composition of the present invention contains 5% by weight or more of a volatile solvent. The amount of the volatile solvent is preferably adjusted so that the solid content of the composition of the present invention is 20 to 50% by weight, more preferably 25 to 35% by weight. The volatile solvent used in the present invention is not particularly limited as long as it is inert to the above components (A), (B) and (C) and has an appropriate volatility.

Specifically, methanol, ethanol, methyl ethyl ketone, ethyl acetate, butyl acetate, cellosolve acetate, mineral spirit, toluene, xylene, dimethylacetamide, acetone, n-hexane,
Examples include methylene chloride, tetrahydrofuran, ethyl ether, dioxane, etc., of which methyl ethyl ketone, ethyl acetate and methanol are preferred. The volatile solvents can be used alone or in combination of two or more. In addition, it is preferable to mix | blend a volatile solvent after drying or dehydrating sufficiently.

In the primer composition of the present invention, a stabilizer may be used in combination with the above essential components in order to further improve the storage stability. The stabilizer is not particularly limited and known stabilizers can be used. In particular, active methylene compounds such as diethyl malonate and monoalcohols such as methyl alcohol and ethyl alcohol are preferable.

The primer composition of the present invention may use a water absorbing agent for the purpose of further improving the storage stability. Examples of the water absorbing agent include synthetic or natural zeolites, and any known water absorbing agent can be used as long as the object of the present invention is not impaired.

As the water-absorbing agent, a zeolite-based water-absorbing agent such as synthetic or natural zeolite is preferable from the viewpoint of water-absorbing ability, and among them, those having a pore diameter of about 3 to 10 mm are preferably used. Preferred specific examples of commercially available zeolites include Bayrit L powder manufactured by Bayer, molecular sieve manufactured by Union Carbide, and zeolam manufactured by Tosoh. The water-absorbing agent may or may not dissolve in the primer of the present invention. If it does not dissolve, the water-absorbing agent may be allowed to coexist with the primer composition.

The primer composition of the present invention may further contain other additives. For example, carbon black,
Inorganic pigments such as lamp black, titanium white, red iron, titanium yellow, zinc white, lead red, cobalt blue, iron black, aluminum powder, etc .; neozabon black RE, neoblack RE, orazole black CN, orazole black Ba (any Organic pigments such as Ciba-Geigy) and Spiron Blue 2BH (Hodogaya Chemical); Siasolve (Cyasorb UV24Light Absorber, American Cyanamid), Ubinul (Uvinul D-49, D-5)
0, N-35, N-539, manufactured by General Aniline Co.)
Or it absorbs and is effective in improving light resistance. further,
Glass powder, clay, powdered silica gel, ultrafine silica powder, molecular sieves (which also has water absorption capacity)
And the like, a thickener, a butyl benzyl phthalate, a dioctyl phthalate, a dibutyl phthalate, a plasticizer which gives flexibility to a primer film such as a paraffin chloride and the like, and improves adhesive strength.

The method for producing the composition of the present invention is not particularly limited, and examples thereof include (A) a silane compound, (B) an organotitanium compound and / or a condensate thereof, (C) a film-forming resin, and (D) a volatile compound. A solvent and, if necessary, other additives may be added and kneaded using a stirring device such as a ball mill until the mixture becomes uniform.

The composition of the present invention thus obtained has excellent adhesiveness to concrete, mortar, PVC steel plate and the like, and also has an excellent balance with storage stability. Therefore, the composition of the present invention is suitably used particularly as a primer used in the fields of civil engineering, architecture and the like.

[0062]

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples. (Examples 1 to 10) Compounds were blended at the weight ratios shown in Table 1 to produce compositions. The obtained composition was evaluated for storage stability and adhesion. Table 1 shows the results.

(1) Storage stability test The obtained composition was stored at 60 ° C in a closed container, and the state after 7 days had elapsed was observed. In Table 1, those that did not undergo gelation or solidification were rated as ○, and those that did undergo gelation or solidification were rated as x.

(2) Adhesion test Using foamed concrete (ALC), mortar, or PVC steel plate as an adherend, the obtained composition is applied to the surface of the adherend, and a polyurethane-based sealant (Yokohama Rubber ("Seal 21" manufactured by Co., Ltd.) was pressed into a test piece. The test piece was stored at 20 ° C. and a relative humidity of 55%, and a peel test was performed 7 days after the application, and the state of the adhesive interface between the adherend and the composition was observed. In Table 1, a sample having no peeling (AF) of the bonding interface was marked with a circle, and the AF area was 1 to 10
% And Δ when the AF area was 20% or more.

(Comparative Examples 1 to 5) The following Comparative Examples 1 to 5 were evaluated for storage stability and adhesion in the same manner as in the Examples. Table 1 shows the results. Comparative Example 1: An example not containing an organic titanium compound and / or a condensate thereof Comparative Example 2: An example in which aminosilane was used alone as a silane compound Comparative Example 3: One type of aminosilane and one epoxysilane as silane compounds Comparative Example 4: Example in which the amount of the organic titanium compound is small Comparative Example 5: Example in which the amount of the organic titanium compound is large

[0066]

[Table 1]

The following components were used for each component in Table 1. (1) Silane compound Silane compound 1: γ-glycidoxypropyltrimethoxysilane (“A187” manufactured by Nippon Unicar Co., Ltd.), γ-glycidoxypropyltrimethoxysilane
Glycidoxypropylmethyldimethoxysilane (“AZ6137” manufactured by Nippon Unicar Co., Ltd.) and N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane (“A1120” manufactured by Nippon Unicar Co., Ltd.) were converted to A187 / A
Z6137 / A1120 = 1.15 / 1.15 / 1.0
A compound obtained by mixing at a ratio of 0 (molar ratio) and reacting at 50 ° C. for 40 hours. After the reaction, methyl ethyl ketone (ME
K) was added to use at a solid concentration of 50% by weight.
Here, the solid content concentration is considered to be substantially equal to the content of the target silane compound 1. The same applies to the following silane compound 3, acrylic resin and epoxy resin.

Silane compound 2: N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane

Silane compound 3: γ-glycidoxypropyltrimethoxysilane (“A18” manufactured by Nippon Unicar Co., Ltd.)
7 "), N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane (" A11 "manufactured by Nippon Unicar Co., Ltd.)
20 ") was calculated as A187 / A1120 = 2.30 / 1.0.
A compound obtained by mixing at a ratio of 0 (molar ratio) and reacting at 50 ° C. for 40 hours. After the reaction, MEK was added to use the solid content concentration at 50% by weight.

(2) Film resin Acrylic resin: MMA (50.0 g), BMA (50.
0g), HEMA (20.0g), and MEK (12
1g), and a mixed solution obtained by further adding azobisisobutyronitrile (1.0 g) at 70 ° C. for 24 hours. MEK was not removed and used as contained. The solid concentration was 50% by weight.

Epoxy resin: bisphenol A type epoxy resin (epoxy equivalent: 850 g / eq, Toto Kasei Co., Ltd.)
MEK to “YD-014” manufactured by Kobe Steel Co., Ltd.
Used as 0% by weight.

Aromatic terpene resin: "TO105" manufactured by Yashara Chemical Co., Ltd. Chlorinated polypropylene: "HP62" manufactured by Nippon Paper Industries Co., Ltd.
0 "Chlorinated polyethylene:" HE55 "manufactured by Nippon Paper Industries Co., Ltd.
0 "

(3) Organotitanium compound and / or condensate thereof Tetra-n-butoxytitanium (organotitanium compound 1):
Matsumoto Pharmaceutical Co., Ltd. "B-1" tetra-n-butoxytitanium decamer (organic titanium compound 2): Matsumoto Pharmaceutical Co., Ltd. "B-10" titanium tetraacetylacetonate (organic titanium compound 3) ): “Orgatics TC-4” manufactured by Matsumoto Pharmaceutical Co., Ltd.
01 "diisopropoxybis (ethylacetoacetate) titanium (organic titanium compound 4):" Orgatics TC-750 "manufactured by Matsumoto Pharmaceutical Co., Ltd. di (2-ethylhexoxy) bis (2-ethyl-1,3)
-Hexanediolate) titanium (organic titanium compound 5): "Orgatics TC-2" manufactured by Matsumoto Pharmaceutical Co., Ltd.
00 "

[0074]

According to the present invention, the adhesiveness to porous substrates such as concrete, mortar and hard PVC is excellent.
In addition, a primer composition having excellent storage stability can be obtained.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroyuki Hosoda 2-1 Oiwake, Hiratsuka-shi, Kanagawa Yokohama Rubber Co., Ltd. Inside the Hiratsuka Factory (72) Inventor Takanobu Otoido 2-1 Oiwake, Hiratsuka-shi, Kanagawa Yokohama Rubber F-term in Hiratsuka Factory (reference) 4J038 CB172 CG002 CR072 DB002 DL051 DL052 DL081 DL082 DM002 EA012 JC38 KA06 NA27 PB05 PC04

Claims (2)

[Claims] 1. A compound having a hydrolyzable silyl group, which is a reaction product of (A) an aminosilane and two types of epoxysilanes having different hydrolysis rates, and (B) an organotitanium compound And / or condensate thereof.
A primer composition comprising 1 to 10% by weight, (C) 2 to 30% by weight of a film-forming resin, and (D) 5% by weight or more of a volatile solvent. 2. The organic group of the (B) organotitanium compound,
The primer composition according to claim 1, wherein the primer composition is selected from the group consisting of an acetylacetone residue, an acetoacetic ester residue, a glycol residue, an alcohol residue, and a carboxylic acid residue.