JPH11209682A - Primer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a primer compsn. which exhibits a very high adhesive power even when exposed to alkaline conditions. SOLUTION: This compsn. comprises (A) an acrylic copolymer having a reactive silyl group and formed from (a) a monomer having a carbon-bonded reactive silyl group represented by the formula (wherein R<1> is H or 1-10C alkyl; R<2> is H, 1-10C alkyl, aryl or aralkyl; and a is 0, 1 or 2), (b) an alkyl(meth) acrylate monomer having a 10C or higher alkyl group, and (c) other copolymerizable monomers and (B) an aminosilane compd. and/or a reaction product thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a plumer composition. More specifically, the present invention relates to a primer composition that is effective for adhesion between various elastic sealing materials and mortar, metal, ceramics, glass, cement, ceramic moldings, plastics, various painted surfaces, and the like.

[0002]

2. Description of the Related Art In recent years, elastic sealing materials have been widely used for buildings, automobiles, etc., but their adhesive performance is still insufficient, and the use of a primer is almost indispensable. I have.

[0003] Particularly, when used around ceramic moldings and concrete, there remains a problem that peeling is likely to occur due to the transfer of alkalinity, which causes a decrease in adhesiveness.

[0004]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies in view of the above situation and as a result, found that a composition comprising an acrylic copolymer containing a specific reactive silyl group was used as a primer. It has been found that by use, it exhibits very high adhesion even when exposed to alkalinity.

That is, the primer composition of the present invention comprises:
It comprises the following components (A) and (B).

(A) Reactive silyl group-containing acrylic copolymer comprising the following monomers a to c: (a) The following general formula (I)

Embedded image (Wherein, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group; a represents an integer of 0 to 2) a monomer containing a reactive silyl group bonded to a carbon atom (reactive silyl group-containing monomer); (b) an alkyl group having 10 or more carbon atoms Having (meta)
Alkyl acrylate monomers, (c) other copolymerizable monomers (B) aminosilane compounds and / or reactants thereof.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Component (A) (containing a reactive silyl group)
Acrylic copolymer) The primer resin composition of the present invention comprises a reactive silyl group-containing monomer (a) and an alkyl group having 10 or more carbon atoms as a base resin having curability at room temperature in the presence of moisture. A reactive silyl group-containing acrylic copolymer (A), which is a copolymer obtained by polymerizing a (meth) acrylic acid alkyl ester monomer (b) and another copolymerizable monomer (c) Component).

[0008] The acrylic copolymer (A) has a main chain substantially consisting of a main chain obtained by copolymerizing an acrylic monomer (hereinafter, also referred to as a case where the main chain substantially consists of an acrylic copolymer chain). ) Is a copolymer and contains a reactive silyl group bonded to a carbon atom, so that the resulting primer formed from the composition of the present invention not only has excellent adhesion, but also has excellent water resistance. It has very good adhesion even when exposed to properties such as alkali resistance.

In the acrylic copolymer (A), the number of reactive silyl groups bonded to carbon atoms represented by the general formula (I) is at least one per molecule of the acrylic copolymer (A), The number is preferably 1 to 15, more preferably 2 to 10, since the primer formed from the composition of the present invention is excellent in adhesive strength, alkali resistance, durability and the like. When the number of reactive silyl groups is less than 1, the adhesive strength tends to be low.

The reactive silyl group represented by the general formula (I) may be bonded to the terminal of the main chain of the acrylic copolymer (A) or may be bonded to a side chain. It may be bonded to the terminal and the side chain of the main chain.

In the above general formula (I), R ¹ is a hydrogen atom or a group having 1 to 10 carbon atoms, preferably, for example, methyl, ethyl, n-propyl, i-propyl, n-propyl.
It is a C1-C4 alkyl group, such as a butyl group and an i-butyl group. If the alkyl group has more than 10 carbon atoms, the reactivity of the reactive silyl group will decrease.
Further, the R ¹ is a phenyl group, even if a group other than an alkyl group such as a benzyl group, the reactivity of the reactive silyl groups will be lowered.

In the general formula (I), R ² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably, for example, an alkyl group having 1 to 4 carbon atoms as exemplified in the aforementioned R ¹ ;
For example, it is a monovalent hydrocarbon group selected from an aryl group preferably having 6 to 25 carbon atoms such as a phenyl group and an aralkyl group preferably having 7 to 12 carbon atoms such as a benzyl group. Among them, an alkyl group having 1 to 4 carbon atoms is preferable from the viewpoint that the composition of the present invention is excellent in curability.

In the above general formula (I), (R ¹ O)
_3-a is selected so that (3-a) becomes 1 or more and 3 or less, that is, a becomes 0 to 2, but the curability of the acrylic copolymer (A) becomes good. From a
Is preferably 0 or 1. Therefore, R ²
Is preferably 0 or 1.

(R ¹ O) present in the general formula (I)
_{When the number of 3-a} or (R ² ) _a is two or more, R ¹ or R ² contained in two or more may be the same or different.

The acrylic copolymer (A) was synthesized using a monomer unit containing a reactive silyl group bonded to a carbon atom represented by the general formula (I) in the molecule. Are preferred. In addition, the content ratio of the monomer unit in the acrylic copolymer (A) is from 1 to 4 in that the primer formed using the composition of the present invention has excellent durability and strength. 30%, and even 2
-20%, particularly preferably 2-15%. When the amount is less than 1%, the curability tends to be insufficient, and when it exceeds 30%, the storage stability tends to decrease.

The number average molecular weight of the acrylic copolymer (A) is determined from the viewpoint that the primer formed using the composition of the present invention has excellent properties such as adhesive strength and durability.
2000 to 50,000, above all 7000 to 25
000 is preferred.

The glass transition temperature of the acrylic copolymer (A) is set at 20 ° C. in view of the fact that the primer formed using the composition of the present invention has excellent physical properties such as dryness to the touch and dust adhesion. The temperature is preferably at least 35 ° C. If the temperature is lower than 20 ° C., the drying property at a low temperature is poor, and the adhesiveness is reduced.

Acrylic copolymer (A) as described above
May be used alone or in combination of two or more.

Next, an example of a method for producing the acrylic copolymer (A) will be described. As described above, the acrylic copolymer (A) has, for example, a monomer (a) containing a polymerizable double bond and a reactive silyl group bonded to a carbon atom, and an alkyl group having 10 or more carbon atoms. (Meta)
It can be produced by polymerizing an alkyl acrylate monomer (b) and another copolymerizable monomer (c).

Monomer (a) Specific examples of the reactive silyl group-containing monomer (a) include, for example,

Embedded image General formula (III) such as:

Embedded image (Wherein R ¹ , R ² and a are the same as above, and R ⁵ represents a hydrogen atom or a methyl group).

[0021]

Embedded image General formula (IV) such as:

Embedded image (In the formula, R ¹ , R ² , R ⁵ and a are the same as described above, and n represents an integer of 1 to 12.)

[0022]

Embedded image General formula (V) such as:

Embedded image (Wherein R ¹ , R ² , R ⁵ , a and n are the same as described above)
A compound represented by the formula:

[0023]

Embedded image General formula (VI) such as:

Embedded image (Wherein R ¹ , R ² , R ⁵ , and a are the same as above, and m is 1 to
Indicates an integer of 14. ).

[0024]

Embedded image (Wherein, p represents an integer of 0 to 20), such as general formula (VII):

Embedded image Etc. can be exemplified.

Monomer (b) Specific examples of the (meth) acrylic acid alkyl ester monomer (b) having an alkyl group having 10 or more carbon atoms include lauryl (meth) acrylate, tridecyl (meth) acrylate and cetyl. (Meth) acrylate, stearyl (meth) acrylate, docosanyl (meth) acrylate, behenyl (meth) acrylate and the like.

The amount of the monomer (b) used is preferably 2 to 30%, more preferably 5 to 25%, and particularly preferably 5 to 20% of the total amount of the commonly used polymerization components. When the amount used is less than 2%, the adhesiveness is hardly developed, and when it exceeds 30%, the compatibility decreases.

Monomer (c) Specific examples of the other copolymerizable monomer (c) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, (meth) acrylonitrile, glycidyl (meth) Acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylamide, α-ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (Meth) acrylamide, N-methyl (meth) acrylamide (meth) acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-methylol (meth) acrylamide, Alonix M-5700, macromonomer AS-6, AN-6, AA-6, AB-6, AK-
5 and the like (these are manufactured by Toa Gosei Chemical Industry Co., Ltd.),
Placel FA-1, Placel FA-
4, Placel FM-1, Placel FM
-4 (manufactured by Daicel Chemical Industries, Ltd.), a phosphate group-containing (meth) acrylic compound such as a condensation product of a hydroxyalkyl ester of (meth) acrylic acid and phosphoric acid or a phosphoric acid ester And a (meth) acrylate containing a urethane bond or a siloxane bond. These monomers (C) may be used alone,
More than one species may be used in combination.

The amount of the monomer (c) used is preferably from 5 to 95%, more preferably from 30 to 90%, particularly preferably from 40 to 85%, of the total amount of the commonly used polymerization components.

In the present invention, for the purpose of further improving the adhesiveness of the primer formed from the obtained composition of the present invention, for example, a segment formed by a urethane bond or a siloxane bond in the main chain is 50% May be introduced at the time of production of the acrylic copolymer (A) within a range not exceeding.

Specific examples of monomers other than the above-mentioned monomers include, for example, aromatic hydrocarbon-based vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, styrenesulfonic acid, 4-hydroxystyrene, and vinyltoluene; Carboxylic acids, such as fumaric acid, itaconic acid, and (meth) acrylic acid; salts thereof, such as alkali metal salts, ammonium salts, and amine salts; acid anhydrides of unsaturated carboxylic acids, such as maleic anhydride; Esters of unsaturated carboxylic acids such as diesters or half esters of anhydrides and alcohols or amines having a linear or branched chain having 1 to 20 carbon atoms; vinyl esters such as vinyl acetate, vinyl propionate and diallyl phthalate; Compounds: vinylpyridine, aminoethyl vinyl ether, etc. Amide group-containing vinyl compounds such as itaconic acid diamide, crotonic amide, maleic acid diamide, fumaric acid diamide, N-vinylpyrrolidone; 2-hydroxyethyl vinyl ether, methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride , Vinylidene chloride, chloroprene, propylene, butadiene, isoprene, fluoroolefin maleimide, N-vinylimidazole, and other vinyl compounds such as vinylsulfonic acid. These may be used alone or in combination of two or more.

The acrylic copolymer (A) is disclosed in, for example, JP-A-54-36395 and JP-A-57-559.
No. 54, etc. can be produced by a hydrosilylation method or a solution polymerization method using a monomer containing a reactive silyl group, but contains a reactive silyl group from the viewpoint of ease of synthesis and the like. It is particularly preferable that the monomer is produced by a solution polymerization method using an azo radical polymerization initiator such as azobisisobutyronitrile using a monomer.

The solvent used in the solution polymerization method is not particularly limited as long as it is a non-aqueous solvent. Examples thereof include hydrocarbons such as toluene, xylene, n-hexane and cyclohexane; and ethyl acetate and butyl acetate. Acetates; cellosolves such as ethyl cellosolve and butyl cellosorb; ether esters such as cellosolve acetate; ketones such as methyl ethyl ketone, ethyl acetoacetate, acetylacetone, methyl isobutyl ketone, acetone; methanol, isopropyl alcohol;
alcohols such as n-butanol, isobutanol, hexanol and octanol;

In the above solution polymerization, if necessary, for example, n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, ( _{CH 3 O) 3 Si-S} -S-S
_{i (OCH 3) 3, (} CH 3 O) 3 Si-S 8 -Si
The molecular weight of the resulting acrylic copolymer (A) may be adjusted by using a chain transfer agent such as (OCH ₃ ) ₃ alone or in combination of two or more. In particular, for example, γ
When a chain transfer agent having an alkoxysilyl group in the molecule, such as -mercaptopropyltrimethoxysilane, is used, a reactive silyl group can be introduced into the terminal of the acrylic copolymer (A). The amount of the chain transfer agent to be used is preferably 0.05 to 10%, more preferably 0.1 to 8% of the total amount of the used polymerization components.

Specific examples of the alkyl alcohol include lower alcohols having 1 to 4 carbon atoms such as methanol and ethanol.

The dehydrating agent and the alkyl alcohol may be added, for example, to the components before the polymerization of the acrylic copolymer (A), or may be added during the polymerization of the acrylic copolymer (A). It may be added at the time of mixing the obtained acrylic copolymer (A) with other components, and there is no particular limitation.

The amount of the dehydrating agent is not particularly limited, but is usually 100% of the resin solid content of the acrylic copolymer (A).
0.5 to 20 parts of dehydrating agent per part, especially 2
It is preferably about 10 to 10 parts.

Specific examples of the dehydrating agent include, for example, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, trimethyl orthopropionate, triethyl orthopropionate, trimethyl orthoisopropionate, triethyl orthoisopropionate. And hydrolysable ester compounds such as trimethyl orthobutyrate, triethyl orthobutyrate, trimethyl orthoisobutyrate and triethyl orthoisobutyrate. Among these, methyl orthoacetate is preferred from the viewpoint of dehydration effect. These may be used alone or in combination of two or more.

The curing catalyst used in the present invention is a carboxylic acid type organic tin compound such as tin octylate, dibutyltin dilaurate, dioctyltin malate, a sulfide type such as monobutyltin sulfide or dioctyltin mercaptide, or a mercaptide type organic tin compound. , Organic tin oxide such as dioctyltin oxide or dibutyltin oxide, organic tin oxide and ethyl silicate, ethyl silicate 4
0, a reaction product with an ester compound such as dimethyl maleate or dioctyl phthalate; phosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monooctyl phosphate, monodecyl phosphate, dimethyl phosphate, Diethyl phosphate, dibutyl phosphate, didecylphosphocyclohexene oxide, glycidyl methacrylate,
Glycidol, acrylic glycidyl ether, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane,

Embedded image Reaction products of epoxy compounds with phosphoric acid and / or monoacidic phosphate such as Cardura E, manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 828, Epicoat 1001, manufactured by Yuka Shell Epoxy Co .; organic titanates Compounds, organoaluminum compounds; maleic acid, adipic acid, azelaic acid, sebacic acid, itaconic acid, citric acid, succinic acid, phthalic acid, trimellitic acid, pyromellitic acid, their acid anhydrides, paratoluenesulfonic acid, etc. Acidic compounds; amines such as hexylamine, di-2-ethylhexylamine, N, N-dimethyldodecylamine and dodecylamine; these amines and acidic amines such as N, N-dimethyldodecylamine and dodecylamine Amines; mixtures of these amines with acidic phosphate esters or Applied Physics; sodium hydroxide, and the like alkaline compound such as potassium hydroxide.

Of these, an organotin compound and a reaction product of an organotin compound and ethyl silicate are preferred in terms of adhesion and curability.

These curing catalysts are used in an amount of 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the acrylic copolymer (A). 0.05 used
If the amount is less than 10 parts by weight, the curability tends to decrease,
If the amount exceeds the weight part, the water resistance tends to decrease.

Component (B) (aminosilane compound and / or
Is a reaction product thereof.) As the component (B) in the present invention, for example, aminoethylaminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyldimethoxysilane, γ-aminopropyltriethoxysilane,
aminosilane compounds such as γ-aminopropyldiethoxysilane; these aminosilane compounds and epicoat 8
28, a reaction product with an epoxy compound such as Epicoat 1001 (both manufactured by Yuka Shell Epoxy Co., Ltd.) and γ-glycidoxypropyltrimethoxysilane (for example, aminosilane (A1 having one amino group in the molecule)
100) and Epicoat 828 which is a bifunctional epoxy compound at a molar ratio of 2: 1, or aminoethylaminopropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane at a molar ratio of 1: 2.2. Mixing at the above ratio and reacting at 70 to 90 ° C. for 2 to 4 hours under a nitrogen stream). These may be used alone or in combination of two or more. Among them, γ-aminopropyltrimethoxysilane, aminoethylaminopropyltrimethoxysilane and γ-aminopropyltrimethoxysilane
A combination of glycidoxypropyltrimethoxysilane with a reactant is preferred from the viewpoint of adhesion.

The amount of component (B) used is 100 parts of component (A).
0.1 to 50 parts by weight, preferably 0.1 to 50 parts by weight
To 30 parts by weight, more preferably 0.5 to 20 parts by weight. If the amount is less than 0.1 part, the improvement of the adhesion becomes insufficient, and if it exceeds 50 parts by weight, the compatibility may be reduced.

As described above, in the present invention, an acrylic polymer having at least one reactive silicon group is used as a primer. It is possible. When used on a wet surface, use of a polar solvent such as an alcohol such as isopropanol or a ketone such as methyl ethyl ketone can further enhance the adhesive performance.

In the present invention, first, a primer is applied on an adherend, a primer layer is formed, and then the curable composition is applied thereon. The method for applying the primer and the method for applying the curable composition are not particularly limited, and widely known coating means such as coating with a brush, coating with a roll, and coating with a spray can be widely used. The amount of the primer to be applied is usually 20 to 40 per 1 m ² area of the adherend.
It is good to be about 0 g, preferably about 40 to 100 g. To form a primer layer on the adherend, after applying the primer, it may be dried at room temperature, or
You may heat at the temperature of about 50-120 degreeC.

Further, the primer composition of the present invention includes:
For example, titanium oxide, ultramarine, navy blue, zinc white, red iron,
Pigments such as inorganic pigments such as graphite, lead white, carbon black, transparent iron oxide, and aluminum powder; organic pigments such as azo pigments, triphenylmethane pigments, quinoline pigments, anthraquinone pigments, and phthalocyanine pigments; Additives such as agents, ultraviolet absorbers, light stabilizers, anti-sagging agents, leveling agents; cellulose such as nitrocellulose, cellulose acetate butyrate; epoxy resins, melamine resins, vinyl chloride resins, fluororesins, chlorinated polypropylene, Resins such as chlorinated rubber, polyvinyl butyral, and polysiloxane may be appropriately added.

The elastic sealing material used in the present invention is not particularly limited, and may be polyurethane-based, polysulfide-based,
Modified silicon type and silicone type can be used.

The composition for plummer of the present invention comprises various elastic sealing materials and mortar, metal, ceramics, glass,
It is suitably used as a primer that is effective for adhesion to cement, ceramic moldings, plastics, various painted surfaces, and the like.

[0048]

EXAMPLES Next, the primer resin composition of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to only these Examples.

Production Example 1 (Acrylic copolymer (A-1)
Production of xylene) 50 parts of xylene was charged into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel,
The temperature was raised to 110 ° C. while introducing nitrogen gas. after that,
2.4 parts of styrene, 6.6 parts of γ-methacryloxypropyltrimethoxysilane, stearyl methacrylate 14
Part, methyl methacrylate 71 parts, n-butyl acrylate 5 parts, acrylamide 1 part, toluene 18 parts and 2,2'-azobisisobutyronitrile 0.8 parts by weight, at a constant speed over 5 hours by a dropping funnel. It was dropped.

After completion of the dropwise addition, 0.1 part of 2,2'-azoisobutyronitrile, 5 parts of xylene and 8 parts of toluene were added to 1 part.
After dropping at a constant speed over a period of time, the mixture was aged at 110 ° C. for 2 hours and cooled. Toluene was added to the resin solution to obtain an acrylic copolymer (A-1) having a resin solid concentration of 30%.

The number average molecular weight of the obtained acrylic copolymer (A-1) was 16,000. The calculated glass transition temperature was 52 ° C.

Production Example 2 (Acrylic copolymer (A-2)
Of a stirrer, a thermometer, a reflux condenser, was charged with 50 parts of xylene to a reaction vessel equipped with a nitrogen gas inlet tube and a dropping funnel,
The temperature was raised to 110 ° C. while introducing nitrogen gas. after that,
5.7 parts of styrene, 3.3 parts of γ-methacryloxypropyltrimethoxysilane, stearyl methacrylate 20
Part, methyl methacrylate 65 parts, n-butyl acrylate 5 parts, acrylamide 1 part, toluene 18 parts and 2,2'-azobisisobutyronitrile 0.5 parts of a mixture composed of a dropping funnel at a constant velocity over 5 hours. It was dropped.

After the completion of the dropwise addition, 0.1 part of 2,2'-azoisobutyronitrile, 5 parts of xylene and 8 parts of toluene were added to 1 part.
After dropping at a constant speed over a period of time, the mixture was aged at 110 ° C. for 2 hours, cooled, and toluene was added to the resin solution to obtain an acrylic copolymer (A-2) having a resin solid content of 30%.

The number average molecular weight of the obtained acrylic copolymer (A-2) was 21,000. The calculated glass transition temperature was 41 ° C.

Production Example 3 (Acrylic copolymer (A-3)
Of a stirrer, a thermometer, a reflux condenser, was charged with 50 parts of xylene to a reaction vessel equipped with a nitrogen gas inlet tube and a dropping funnel,
The temperature was raised to 110 ° C. while introducing nitrogen gas. after that,
2.4 parts of styrene, 6.6 parts of γ-methacryloxypropyltrimethoxysilane, lauryl methacrylate 10
Part, methyl methacrylate 71 parts, n-butyl acrylate 9 parts, acrylamide 1 part, toluene 18 parts and 2,2'-azobisisobutyronitrile 0.8 parts by weight, using a dropping funnel over 5 hours at a constant velocity. It was dropped.

After the completion of the dropwise addition, 0.1 part of 2,2'-azoisobutyronitrile, 5 parts of xylene and 8 parts of toluene were added to 1 part.
After dropping at a constant speed over a period of time, the mixture was aged at 110 ° C. for 2 hours and then cooled. Toluene was added to the resin solution to obtain an acrylic copolymer (A-3) having a resin solid concentration of 30%.

The obtained acrylic copolymer (A-3) had a number average molecular weight of 15,000. The calculated glass transition temperature was 53 ° C.

Production Example 4 (Production of Elastic Sealant) Propylene oxide having a number average molecular weight of 17,000 and an average of 2.1 methyldimethoxysilyl groups [—Si (CH ₃ ) (OCH ₃ ) ₂ ] per molecule 100 parts by weight of a polymer, 55 parts by weight of DIDP (diisodecyl phthalate) as a plasticizer, 100 parts by weight of surface-treated colloidal calcium carbonate as a filler, 20 parts by weight of titanium oxide, 2 parts by weight of an aliphatic amide wax as an anti-sagging agent, and an ultraviolet absorber 1 part by weight of Tinuvin 327 (manufactured by Ciba-Geigy), 1 part by weight of Tinuvin 770 (manufactured by Ciba-Geigy), 2 parts by weight of vinyltrimethoxysilane as a dehydrating agent, and A1120 (aminosilane, manufactured by Nippon Unicar, Inc.) as an adhesion improver ), U-220 as a curing catalyst
After adding 2 parts by weight (manufactured by Nitto Kasei) and kneading well,
The mixture was passed three times through a small three paint roll to obtain a curable composition.

Examples 1 to 5 and Comparative Example 1 Acrylic copolymers (A-1) obtained in Production Examples 1 to 3
Table 1 with respect to 100 parts by weight of the resin solid content of (A-3)
The primers were obtained by blending various additives shown in (1) and (2).

The primer thus obtained was applied to electrolytically colored aluminum (50 × 50 × 5 mm) in an atmosphere of 23 ° C., dried for 1 hour, and then assembled in a frame as shown in FIG.
The elastic sealing obtained in the above was filled. It was left to stand in an atmosphere of 23 ° C. for 7 days and then at 50 ° C. for 7 days to be cured to obtain an H-shaped sample for tensile adhesion as shown in FIG.

The obtained H-type sample for tensile adhesion was immersed in a saturated aqueous solution of calcium hydroxide at 60 ° C. for 7 days, taken out, and subjected to a tensile test to find a 50% modulus (M5
0, Kgf / cm ² ), strength at break (TB, Kgf / c)
m ² ) and elongation at break (EB,%) were measured.

[0062]

[Table 1]

[0063]

According to the present invention, it is possible to provide a primer composition exhibiting extremely high adhesive strength even when exposed to alkalinity.

[Brief description of the drawings]

FIG. 1 shows a frame used in this example and a comparative example.

FIG. 2 shows the shape of an H-shaped sample for tensile adhesion obtained in this example and a comparative example.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 33:00

Claims (5)

[Claims] 1. A primer composition comprising the following components (A) and (B): (A) Reactive silyl group-containing acrylic copolymer comprising the following monomers a to c (a) The following general formula (I) (Wherein, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group; a represents an integer of 0 to 2), and a monomer containing a reactive silyl group bonded to a carbon atom (b) having an alkyl group having 10 or more carbon atoms (meth)
Acrylic acid alkyl ester monomer (c) Other copolymerizable monomer (B) Aminosilane compound and / or its reaction product. 2. The method according to claim 1, wherein said monomer (b) is 2 to 2 of the total amount of the polymerization components.
The primer composition according to claim 1, which contains 30%. 3. The glass transition temperature of the component (A) is 35 ° C.
The primer composition according to claim 1 or 2, wherein: 4. The primer composition according to claim 1, wherein the component (B) is a reaction product of an aminosilane compound and an epoxysilane compound or an epoxy resin. 5. A bonding method, comprising applying an elastic sealant after applying the primer composition according to any one of claims 1 to 4.