JP2001172567A - Primer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a primer composition which may be widely applicable to adherends having porous surface structures such as mortar, concrete, etc., exerts an excellent slip resistance and shows an excellent curability at the interface between a sealing material which essentially comprises a saturated hydrocarbon polymer. SOLUTION: The primer composition contains a polyisobutylene having a terminal silyl group or a polysiloxane compound which possesses a hydrolyzable silyl group, a polyisobutylene structure and a siloxane bond and has a polymerization degree of >=20, one or more components selected from the following components (i)-(iii), a silanol condensation catalyst and an organic solvent. (i) A compound of formula (1) and a silane coupling agent, (ii) a compound of formula (2), (iii) the component (ii) and a compound having a isocyanurate ring and at least one alkoxysilyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a primer composition having excellent adhesion at the interface between a primer and a sealing material. The present invention also relates to a primer composition applicable to adherends having a porous surface morphology such as mortar and concrete. The present invention also relates to a primer composition having excellent slip resistance.

[0002]

2. Description of the Related Art Organic polymers, such as polyisobutylene, having a saturated hydrocarbon as a skeleton and having a reactive functional group, are characterized by their excellent weather resistance, heat resistance, and water resistance. It is suitably used for sealants and the like.

However, there is a problem in adhesion due to the non-polarity of the saturated hydrocarbon polymer, and the use of a primer is essential. As the primer, JP-A-11-20970
No. 1, JP-A-11-209702, a method using a saturated hydrocarbon polymer as a binder component, and JP-A-4-252283, a method using an epoxy resin. The publication discloses a method using an additive such as silica.

Further, Japanese Patent Publication No. 6-6680 proposes a primer containing a reactive silicone resin and a specific amino group-containing alkoxysilane with the aim of improving the adhesion to silicones and the like. In addition, Japanese Patent Application Laid-Open
JP-A-95656 proposes a primer containing a specific silicon compound for the purpose of improving the adhesion to the coating film surface with an acrylic electrodeposition paint or a fluororesin paint. There has been no example of a primer that can cover all kinds of adherends, such as a porous adherend such as mortar and concrete.

[0005] The primer for bonding the nonpolar saturated hydrocarbon polymer to various adherends inevitably contains a plasticizer in order to increase the compatibility with the saturated hydrocarbon polymer. And a slip phenomenon such as peeling while maintaining the shape of the coating before the coating is cured is likely to occur.

Further, as a primer composition aiming at improving the adhesiveness to an adherend such as an acrylic resin or a fluorine-based paint having poor adhesion, addition of a primary aminosilane is one of the most effective means. However, when such a primary aminosilane is contained, there is a risk that the composition may cause poor curing at the interface between the primer and the sealing material, retardation of curing, and the like in the initial stage of curing.

For example, when the primer composition is used in a building constructed with a glass run or a curtain wall,
Movement is always occurring at the interface between the primer and the sealing material, and the curing of the interface is delayed. The sealing material is already in a state of exhibiting rubber elasticity, and has a problem that peeling is likely to occur from an uncured interface portion.

On the other hand, in order to effectively utilize the excellent properties of silicone such as heat resistance, oxidation resistance, weather resistance, and adhesion, a vinyl polymer component such as glycol, acrylic or styrene is graft-polymerized. Attempts have been made to provide various properties.

For example, Japanese Patent Application Laid-Open No. 10-36460 discloses an invention in which a monomer having an ethylenically unsaturated bond is graft-polymerized on silicone.
JP-A-279031 discloses a method of graft-polymerizing an oxyalkylene group-containing organic compound onto a silicon-bonded hydrogen atom-containing silicone. In addition, Japanese Patent Laid-Open No. 7-1
No. 8036 discloses a silicone graft copolymer in which a radically polymerizable monomer is graft-polymerized to an iodine-containing silicone polymer.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a mortar having a porous surface morphology when a primer is used for adhesion between a sealing material mainly containing a saturated hydrocarbon polymer and various adherends. An object of the present invention is to provide a primer composition which can be widely applied to concrete and the like, has excellent slip resistance, and can solve problems such as poor curing and delayed curing at the interface between the primer and the sealing material.

The present inventors have conducted intensive studies and have found that by using a silicone graft polymer having excellent properties as a binder component, the silicone graft polymer can be applied to a sealing material mainly containing a saturated hydrocarbon polymer. And a primer composition which can overcome the above-mentioned problems by containing various additives according to the purpose.

[0012]

That is, the present invention relates to a polyisobutylene having a silyl group at a terminal and the following (i):
To (iii) a primer composition comprising: a silanol condensation catalyst; and an organic solvent. (I) a compound represented by the following formula (1) and a silane coupling agent (ii) a compound represented by the following formula (2) (iii) the above (ii) and at least one isocyanurate ring Compound having an alkoxysilyl group

[0013]

Embedded image In the formula, n is an integer of 2 to 8, and R ¹ , R ² and R ³
Is a methyl group or an ethyl group.

The present invention also provides a polymer having a degree of polymerization of 20 or more, having a hydrolyzable silyl group, a polyisobutylene structure and a siloxane bond, one or more of the above (i) to (iii), Provided is a primer composition comprising a condensation catalyst and an organic solvent.

The present invention further provides a polysiloxane compound having a siloxane structure represented by the following formula (3) and / or a polysiloxane compound having a siloxane structure represented by the following formula (4): A primer composition comprising at least one selected member, one or more of the above (i) to (iii), a silanol condensation catalyst, and an organic solvent is provided.

[0016]

Embedded image In the formulas (3) and (4), X is polyisobutylene optionally having a terminal silyl group, and Y is an alkyl group having 1 to 18 carbon atoms optionally having a terminal silyl group. is there. Z is a hydrolyzable group. a, b, c, d, and e are integers, and a / a + b = 0.01 to 0.9, b / a +
b = 0.01 to 0.7, c / c + d + e = 0.01 to
0.7, d / c + d + e = 0.01-0.9, and e /
c + d + e = 0.01 to 0.9, and d and e may be each independently 0.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. 1. The primer composition of the present invention comprises, as a binder component, polyisobutylene having a terminal silyl group, a polymer having a hydrolyzable silyl group, a polyisobutylene structure and a siloxane bond, having a degree of polymerization of 20 or more; 3) a polysiloxane compound having a siloxane structure represented by (hereinafter, referred to as polysiloxane compound (A)) and / or a polysiloxane compound having a siloxane structure represented by the above formula (4) (hereinafter, referred to as
At least one member selected from the group consisting of polysiloxane compounds (B). Hereinafter, each will be described.

Polyisobutylene Having a Silyl Group at the Terminal The polyisobutylene used in the present invention has a silyl group represented by the following formula (5) at the terminal.

[0019]

Embedded image

In the formula (5), R ⁴ , R ⁵ and R ⁶ may be different or the same, and are preferably a hydrolyzable group. Specifically, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, an alkenyloxy group and the like are preferably exemplified. In particular, an alkoxy group is preferable in terms of mild hydrolysis and easy handling, and a methoxy group and an ethoxy group are particularly preferable.

The number average molecular weight of the above polyisobutylene is
A liquid polyisobutylene having a molecular weight of 300 to 30,000 is preferable in terms of solubility, tackiness, and the like. In particular,
EPION (E100S, E103) manufactured by Kanegafuchi Chemical Industry Co., Ltd.
S, E303S, E505S) (product names).

Hydrolyzable silyl group, polyisobutylene structure
Having a polymerization degree of 20 or more
Rimmer The polymer may also be either one kind or two or more kinds, the hydrolyzable silyl group or polyisobutylene structure, may of the also has the side chain of the polysiloxane compound,
When the polysiloxane compound does not have any of these, a compound containing either or both of them may be added to mix the two in the primer composition.

When the polysiloxane compound has a hydrolyzable silyl group or a polyisobutylene structure in the side chain,
A polysiloxane compound having both of these at the same time can be used. In this case, the degree of polymerization of the polysiloxane compound is 20 or more. Further, each of the polysiloxane compounds having one of them in the side chain may be contained in the composition. In this case, the degree of polymerization of each polysiloxane compound is 20 or more in total. Further, by containing a polysiloxane compound having one of them in a side chain and having a degree of polymerization of 20 or more, and a compound having a hydrolyzable silyl group or / and a polyisobutylene structure, both components are contained in the composition. May be mixed. As the polysiloxane compound, a polysiloxane compound (A) or a polysiloxane compound (B) described below is preferable.

Polysiloxane Compound (A) The polysiloxane compound (A) has a structure represented by the above formula (3). In the formula (3), X is polyisobutylene and has a silyl group at a terminal. May be. The silyl group is preferably a group represented by the above formula (5).

Therefore, X may have a hydrolyzable silicon group or an unsaturated group such as trimethoxysilane, triethoxysilane, dimethoxysilane or diethoxysilane at the terminal, and has a number average molecular weight of 300 to 30. , 00
A monovalent polyisobutylene of 0 is preferably used.

The arrangement of each siloxane structure in the molecule is not particularly limited, and the degree of polymerization of the siloxane structure is 20 or more.
These are included in the following composition ratios. That is, a and b in the formula are integers, preferably a is 1 to 200, b is 1 to 200, and more preferably a is 1
50, b is 1 to 50, and a / a + b = 0.01 to
0.9, b / a + b = 0.01 to 0.7. Within this range, the compatibility of the composition of the present invention used as a primer is good, and the adhesiveness of polyisobutylene, aging resistance, ozone resistance, gas impermeability, various excellent properties such as heat resistance, etc. Characteristics can be sufficiently imparted.

Polysiloxane Compound (B) The polysiloxane compound (B) has a structure represented by the above formula (4), wherein X in the formula (4) has the same meaning as X in the above formula (3). It is. Y is an alkyl group having 1 to 18 carbon atoms which may have a silyl group at the terminal.

The silyl group is preferably a compound represented by the above formula (5). When Y has a hydrolyzable silyl group represented by the above formula (5), the adhesion of the primer composition of the present invention containing the polysiloxane compound (B) to an adherend is improved. As Y, specifically, monovalent trimethoxyethylsilane or monovalent triethoxyethylsilane is preferably exemplified.

Z is a hydrolyzable group. The primer composition of the present invention having the polysiloxane compound (B) is
Having in the side chain further improves the adhesion to the adherend. The hydrolyzable group is not particularly limited, but specific examples thereof include a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. You. In particular, an alkoxy group is preferable because it has mild hydrolyzability and is easy to handle.

As the alkoxy group, one having 1 to 3 carbon atoms is preferable, and examples thereof include a methoxy group, an ethoxy group, an n-propyloxy group and an isopropyloxy group. In addition, monovalent ethylene glycol monomethyl ether,
Ether compounds having a hydroxyl group such as divalent diethylene glycol monomethyl ether can also be exemplified. In particular, monovalent ethylene glycol monomethyl ether is preferable.

In the polysiloxane compound (B),
The arrangement of each siloxane structure in the molecule is not particularly limited, and the degree of polymerization of the siloxane structure is 20 or more. These are included in the following composition ratios. That is, c, d, and e in the formula (4) are integers, and preferably, c is 1 to 20.
0, d is 0 to 200, e is 0 to 200, more preferably c is 1 to 50, d is 0 to 100, and e is 0 to 100, and these are c / c + d + e = 0.01 to 0. .7,
d / c + d + e = 0.01 to 0.9, e / c + d + e =
It is in the range of 0.01 to 0.9, and d and e may each independently be 0. Within this range, as in the case of using the polysiloxane compound (A) as the primer, an excellent cured product is obtained, and the warm water resistance is further improved.

The polysiloxane compound (A) or (B) may be used alone or in combination of two or more, but the number average molecular weight is from 500 to 100,000.
It is preferably about 0, especially 1,000 to 30,
Those having a liquid or fluidity of about 000 are preferred.

As the polysiloxane compound, a compound having the following structure is preferably exemplified.

[0034]

Embedded image

In the composition of the present invention, the polysiloxane compounds (A) and (B) may be used in combination. In this case, the ratio of (A) :( B) is 0.1: 10. -10:
It is preferably 0.1, and it is preferable that both are uniformly dispersed and compatible in a solvent.

Polysiloxane compounds (A) and (B)
Are synthesized, for example, by reacting a polysiloxane having an Si-H group with a corresponding alcohol or polyisobutylene or an alkyl group having at least one alkenyl group in a molecule under a transition metal catalyst such as chloroplatinic acid. be able to.

2. The primer composition of the present invention contains any one or more of the following (i) to (iii). (I) a compound represented by the formula (1) and a silane coupling agent (ii) a compound represented by the formula (2) (iii) the (ii) and an isocyanurate ring and at least one alkoxysilyl group And a compound having

Hereinafter, each of them will be described in detail. (I) Compound represented by formula (1) and silane cup
As the ring agent (i), a compound represented by the following formula (1) and a silane coupling agent are used in combination. By selecting (i), in particular, there is an effect that the adhesiveness and adhesion to silicones are improved, and a slip phenomenon is less likely to occur.

[0039]

Embedded image In the formula (1), n is an integer of 2 to 8, and R ¹ and R ² are a methyl group or an ethyl group. When n and R ¹ , R ² are within the above ranges, they are easily available without toxicity problems.

Since the compound represented by the above formula (1) has a very high reactivity, by adding a small amount of such a compound, the saturated hydrocarbon contained in the sealing material is hardened before the sealing material hardens. By reacting with the system polymer, a slip phenomenon at the interface between the primer and the sealing material can be prevented.

The compounding amount of the compound represented by the above formula (1) is such that the above polyisobutylene, polymer or polysiloxane compound is added in a range of 0.1 to 15 parts by weight with respect to 10 parts by weight in total. Is appropriate. Within this range, the effect of the slip resistance can be sufficiently obtained.

As the silane coupling agent, for example,
γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, aminosilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ -Mercaptopropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ-
Examples thereof include chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, and trimethylchlorosilane. In particular, aminosilane, epoxysilane, or a mixture of both is excellent in the effect of improving the adhesiveness to a wet surface and is more preferably used because it is widely used. These may be used alone or in combination of two or more.

The amount of the silane coupling agent is as follows:
It is appropriate to mix the polyisobutylene, polymer, or polysiloxane compound in a range of 1 to 20 parts by weight with respect to 10 parts by weight in total. Within this range, the breaking rate of the sealing material is high with respect to the adhesion to the wet surface.

(Ii) The compound (ii) represented by the formula (2) contains a compound represented by the following formula (2).

[0045]

Embedded image In the formula (2), R ³ is a methyl group or an ethyl group.

By using the compound represented by the above formula (2) as compared with the case of using a primary aminosilane, which has been widely used as a silane coupling agent, curing at the interface with a primer, especially a sealing material, Has an effect of not causing poor curing or delayed curing in the initial stage of the process. As the compound represented by the formula (2), in particular, N-
Phenyl-γ-aminopropyltrimethoxysilane is preferred.

The amount of the compound represented by the above formula (2) is from 1 to 2 parts by weight based on 10 parts by weight of the above polyisobutylene, polymer or polysiloxane compound.
It is appropriate to mix within the range of 0 parts by weight. Within this range, a sufficient effect can be obtained with respect to the curability of the interface between the primer and the sealing material.

(Iii) The above (ii) and isocyanurate
Having a salt ring and at least one alkoxysilyl group
In the compound (iii), a compound having an isocyanurate ring and at least one alkoxysilyl group is used in addition to the compound of the above (ii). When (iii) is selected, the reactivity of the primer composition is increased, and the primer composition has a wide applicability that can be used for adherends having a porous surface morphology such as mortar and concrete.

The compound having an isocyanurate ring and at least one alkoxysilyl group is, for example, a reaction product of isocyanurate silane or a polyisocyanate compound having an isocyanurate ring with a silane coupling agent such as mercaptosilane or aminosilane. Among them, isocyanurate silane having high reactivity and low viscosity is particularly preferable.

The compound having an isocyanurate ring as described above has a very high polarity, so that it is hardly compatible with a nonpolar polyisobutylene or silicone polymer.
Coexistence can be achieved by increasing the content of the solvent.

As the solvent evaporates, the binder component and the above-mentioned compound having an isocyanurate ring undergo phase separation, while the compound having an isocyanurate ring is effective on a porous surface such as mortar or concrete. Can function.

In (iii), the compound of (ii) is added to the isocyanurate ring in an amount of at least 1 to 20 parts by weight based on 10 parts by weight of the polyisobutylene, polymer or polysiloxane compound in total. It is appropriate to compound a compound having one alkoxysilyl group in a range of 1 to 10 parts by weight. Within this range, there is sufficient adhesion to the adherend having a porous surface morphology, and there is no problem with compatibility with the binder component.

3. Silanol condensation catalyst The primer composition of the present invention contains a silanol condensation catalyst. In the present invention, the silanol condensation catalyst is preferably a silane coupling agent of the above (i) having a hydrolyzable silyl group, a compound represented by the formula (2), or an isocyanurate ring and at least one alkoxysilyl. However, when the polysiloxane compound has a hydrolyzable silyl group in the side chain, it can also function as a catalyst, and the cross-linking reaction is carried out. Promoted.

As the silanol condensation catalyst, conventionally known ones can be used as long as the object of the present invention is not impaired. For example, metal salts of organic carboxylic acids such as tin octylate, tin stearate, iron naphthenate, tin octylate, di-n-butyltin-di-laurate, di-n-
Examples thereof include tetravalent organic tin such as butyltin-di-laurate, amines such as laurylamine and ethanolamine, and organic titanates. These may be used alone or in combination of two or more. In particular, organotin, in terms of storage stability and curability,
Organic titanates are preferred.

The amount of the silanol condensation catalyst is within the range of 0.01 to 10 parts by weight based on the total of 10 parts by weight of the polysiloxane compound having a hydrolyzable silyl group and the silane coupling agent. It is appropriate to mix with.

4. Organic Solvent The primer composition of the present invention contains an organic solvent so that the above-mentioned components are uniformly dispersed and form a uniform coating film when applied to an adherend. The organic solvent is not particularly limited as long as the binder components such as the above-mentioned polyisobutylene and polysiloxane compounds (A) and (B) are easily dissolved and inert to these components.

Specifically, aromatic hydrocarbons such as benzene, xylene and toluene, aliphatic hydrocarbons such as n-hexane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, methyl acetate, ethyl acetate and butyl acetate Such as esters, diethyl ether, tetrahydrofuran, ethers such as dioxane, dichloromethane,
Examples include halogenated hydrocarbons such as chloroform and 1,2-dichloroethane, and phenols such as phenol and p-cresol. These may be used alone or in combination of two or more, but it is preferable to use a mixed solution of n-hexane and xylene having appropriate volatility.

The compounding amount of the organic solvent is such that the total amount of the above polyisobutylene, polymer or polysiloxane compound is 1
The total amount is preferably in the range of 30 to 500 parts by weight with respect to 0 parts by weight. Within this range, the components are sufficiently uniformly dispersed.

The primer composition of the present invention may further contain a rust preventive, a plasticizer, a filler, a thickener, an antioxidant, an inorganic pigment, and
Components such as an organic pigment, an ultraviolet absorber, a water absorbing agent, and a thixotropic agent may be blended.

Examples of the rust preventive include various rust preventive pigments, zinc phosphate, tannic acid derivatives, phosphates, and basic sulfonates. Examples of the plasticizer include phthalic acid ester, adipic acid ester, sebacic acid ester and tricresyl phosphate. Fillers include calcium carbonate, carbon black, glass powder,
Clay, powdered silica gel, ultrafine silica powder, molecular sieves and the like can be mentioned.

The method for producing the primer composition of the present invention is not particularly limited. For example, the above-mentioned essential components and other additives are appropriately added to a reaction vessel, and a mixing device such as a ball mill is used. And sufficiently kneaded, and uniformly dispersed to obtain a composition.

The primer composition thus obtained is excellent in tackiness and adhesion, and the obtained cured product has the excellent properties of polyisobutylene and silicone, heat resistance, and oxidation resistance. , Weather resistance, aging resistance,
Excellent in warm water resistance, moisture resistance and electrical properties.

Further, by containing any of the above (i) to (iii), when (i) is included, the effect of preventing the slip phenomenon at the interface between the primer and the sealing material can be obtained by (ii) In the case of containing (iii), the effect of eliminating the above-mentioned problems such as poor curing of the interface and delay in curing, and (iii)
) Has the effect of further improving the adhesion and adhesion to various adherends, including adherends having a porous surface morphology.

[0064]

EXAMPLES The present invention will be described below with reference to examples.
These are shown as an example, and the present invention is not limited by these.

When (i) is included (Examples 1 to 3): a polyisobutylene or polysiloxane compound having a silyl group at a terminal, a compound represented by the above formula (1), a silane coupling agent, a silanol condensation catalyst, an organic compound The solvent was blended with the composition shown in Table 1 and kneaded uniformly to obtain a primer composition.

Comparative Examples 1 to 3 Except that the compound represented by the above formula (1) was not contained, a primer composition was obtained in the same manner as in Example.

<Adhesion Test 1> The primer compositions obtained in Examples and Comparative Examples were applied to an aluminum plate, a glass plate, an acrylic electrodeposited copper plate, a fluorine-baked copper plate, and a two-part silicone sealant, and cured. Thereafter, a sealing material having the composition shown in Table 2 was applied to a thickness of 6 mm, and 20
After leaving for 10 days under conditions of 55 ° C. and 55% RH, they were peeled off by hand, and the adhesion was evaluated. The test method was performed in accordance with the simple adhesion test method described in the Building Sealant Handbook (edited by the Japan Sealant Manufacturers Association).

The criteria for the judgment are as follows. ：: Sealing material rupture ：: Thin layer peeling ×: Peeling at interface 界面: Mixed.

<Evaluation of Slip Resistance> Subsequently, in the same manner as in the above-mentioned adhesion test, the obtained primer composition was filled in a grooved container for a slump test, and after curing, a sealing material was applied to determine the slip resistance according to JIS A1439. Evaluation was made at an average temperature of 50 ° C. ± 2 ° C. by using the groove-shaped container described in 4.4.1 (width 20 mm, depth 10 mm) vertically. The criteria for the determination are as follows. ：: Slip 1 mm or less ×: Slip more than 1 mm Table 1 shows the results.

[0070]

[Table 1]

<Each component in Table 1> Polyisobutylene: PIB oligomer 1 with terminal silane modification
A composition containing 50 parts by weight of process oil with respect to 00 parts by weight, EPION-E100S (manufactured by Kaneka Chemical Co., Ltd.) Polysiloxane compound 1: a polysiloxane compound represented by the following formula

[0072]

Embedded image

Hydrolyzable silicone resin: The following compound,
MS-51 (Mitsubishi Chemical Corporation)

[0074]

Embedded image

Silane coupling agent: aminosilane A1
110, (manufactured by Nippon Unicar Co., Ltd.) Silanol condensation catalyst 1: organic titanate, TPT-10
0 (manufactured by Nippon Soda Co., Ltd.) Silanol condensation catalyst 2: tin compound, SCAT ^# 27
Solvent 1: n-hexane (Kanto Chemical Co., Ltd.) Solvent 2: Xylene (Kanto Chemical Co., Ltd.)

[0076]

[Table 2]

<Each component in Table 2> Polyisobutylene: PIB oligomer 1 with terminal silane modification
EPION505S (manufactured by Kanegafuchi Chemical Co., Ltd.) Process oil: PAO5004 (Idemitsu Petrochemical Co., Ltd.)
Fatty acid-treated calcium carbonate: Sealets 200 (Maruo Calcium Co., Ltd.) Heavy calcium carbonate: Super S (Maruo Calcium Co., Ltd.) Epoxy resin: Bisphenol A type epoxy resin, Epicoat 828 (Yuoka Shell Epoxy Co., Ltd.) Thixotropic agent: hydrogenated castor oil-based thixotropic agent, Dispalon ^# 305
(Kusumoto Kasei Co., Ltd.) Antioxidant 1: Tinuvin 327 (Ciba Geigy Co., Ltd.)
Antioxidant 2: Sanol LS770 (manufactured by Ciba-Geigy) Antioxidant 3: Irganox 1010 (manufactured by Ciba-Geigy) Laurylamine: Farmin 20D (manufactured by Kao Corporation) Tin catalyst: divalent tin Compound, Neostan U-28 (Nitto Kasei Co., Ltd.)

As is clear from Table 1, it can be seen that the inclusion of the hydrolyzable silicone resin improves the slip resistance.

When (ii) was selected (Examples 4 to 6) The components shown in Table 3 were blended and uniformly kneaded to obtain a primer composition.

Comparative Examples 4 to 6 Primer compositions were obtained in the same manner as in Examples 4 to 6 except that phenylaminosilane (N-phenyl-γ-aminopropyltrimethoxysilane) was not contained.

<Adhesion Test 2> In the same manner as in the above-mentioned adhesion test 1, the adhesion of the obtained primer composition was evaluated.

<Interfacial Adhesion> Subsequently, in the same manner as in the above-mentioned adhesion test, the obtained primer composition was applied to each adherend, and after curing, a sealing material was applied. Sealing Material Handbook (edited by the Japan Sealing Material Industry Association)
After 1.5 days at 20 ° C. and 55% RH, it was peeled off by hand and evaluated. The criteria for the determination are as follows. ：: No uncured phenomenon occurred. X: Uncured. Table 3 shows the results.

[0083]

[Table 3]

<Each component in Table 3> Polyisobutylene: The same as in Table 1 is used. Polysiloxane compound 1: The same as in Table 1 is used. Polysiloxane compound 2: Polysiloxane compound represented by the following formula

[0085]

Embedded image

Silane coupling agent: Use the same as in Table 1. Phenylaminosilane: Aminosilane Y9669 (manufactured by Nippon Unicar Co.) Silanol condensation catalyst 1: Use the same as in Table 1 Solvent 1: Use the same as in Table 1 Solvent 2: Use the same as in Table 1.

As apparent from Table 3, the adhesiveness at the interface was improved by containing phenylaminosilane (N-phenyl-γ-aminopropyltrimethoxysilane).

When (iii) was selected (Examples 7 to 9) Each component was blended with the composition shown in Table 4 and uniformly kneaded to obtain a primer composition.

Comparative Examples 7 to 9 Primer compositions were obtained in the same manner as in Examples except that no isocyanurate silane (compound having an isocyanurate ring and at least one alkoxy group) was contained.

<Adhesion Test 3> Adhesion was evaluated in the same manner as in Adhesion Test 1, except that an acryl urethane baked copper plate, stainless steel, and mortar were added as adherends.

[0091]

[Table 4]

<Each component in Table 4> Polyisobutylene: The same as in Table 1 was used. Polysiloxane compound 1: The same as in Table 1 was used. Polysiloxane compound 2: The same as in Table 1 was used. Phenylaminosilane: Use the same one as in Table 1. Isocyanurate silane: aminosilane Y11597
(Manufactured by Nippon Unicar Co., Ltd.) Silanol condensation catalyst 1: Use the same as in Table 1. Solvent 1: Use the same as in Table 1. Solvent 2: Use the same as in Table 1.

As is clear from Table 4, the adhesion to adherends having different surface morphologies was improved by containing isocyanurate silane (compound having an isocyanurate ring and at least one alkoxy group). .

[0094]

As described in detail above, the primer composition of the present invention contains a hydrolyzable silyl group and polyisobutylene as binder components to improve the adhesion and adhesion to various adherends. I do. In addition, specific effects can be obtained by containing the following (i) to (iii) in addition to the binder component. (I) a compound represented by the formula (1) and a silane coupling agent (ii) a compound represented by the formula (2) (iii) the (ii) and an isocyanurate ring and at least one alkoxy group And a compound having

[0095]

Embedded image In the formula, n is an integer of 2 to 8, and R ¹ , R ² and R ³
Is a methyl group or an ethyl group.

That is, when (i) is contained, the effect of preventing a slip phenomenon that the coating film of the primer is peeled off while maintaining its shape is obtained, and when (ii) is contained, the primer and the sealing material are separated from each other. The effect of eliminating poor curing and delay of curing at the interface is obtained, and
When (iii) is contained, an effect of having excellent adhesion to a porous adherend such as mortar or concrete can be obtained. Such a composition, when the sealing material is used as a primer of a polyisobutylene-based saturated hydrocarbon polymer, the obtained cured product has heat resistance, oxidation resistance, weather resistance, aging resistance, hot water resistance. Excellent in water resistance, moisture resistance and electrical properties.

Claims (3)

[Claims] 1. A primer comprising a polyisobutylene having a silyl group at a terminal, at least one of the following (i) to (iii), a silanol condensation catalyst, and an organic solvent: Composition. (I) a compound represented by the following formula (1) and a silane coupling agent (ii) a compound represented by the following formula (2) (iii) the above (ii) and at least one isocyanurate ring Compound having an alkoxysilyl group embedded image In the formula, n is an integer of 2 to 8, and R ¹ , R ² and R ³
Is a methyl group or an ethyl group. 2. A polymer having a degree of polymerization of 20 or more, having a hydrolyzable silyl group, a polyisobutylene structure and a siloxane bond, at least one of the following (i) to (iii), and a silanol condensation catalyst: A primer composition comprising: an organic solvent. (I) a compound represented by the following formula (1) and a silane coupling agent (ii) a compound represented by the following formula (2) (iii) the above (ii) and at least one isocyanurate ring Compound having an alkoxysilyl group embedded image In the formula, n is an integer of 2 to 8, and R ¹ , R ² and R ³
Is a methyl group or an ethyl group. 3. A polysiloxane compound having a siloxane structure represented by the following formula (3) and / or at least one selected from the group consisting of a polysiloxane compound having a siloxane structure represented by the following formula (4): A primer composition comprising: at least one of the following (i) to (iii): a silanol condensation catalyst; and an organic solvent. (I) a compound represented by the following formula (1) and a silane coupling agent (ii) a compound represented by the following formula (2) (iii) the above (ii) and at least one isocyanurate ring Compound having an alkoxysilyl group embedded image In the formulas (3) and (4), X is a polyisobutylene optionally having a terminal silyl group, and Y is an alkyl group having 1 to 18 carbon atoms optionally having a terminal silyl group. Also,
Z is a hydrolyzable group. a, b, c, d, and e are integers, and a / a + b = 0.01 to 0.9 and b / a + b =
0.01-0.7, c / c + d + e = 0.01-0.
7, d / c + d + e = 0 to 0.9, and e / c + d + e
= 0 to 0.9. Embedded image In the formula, n is an integer of 2 to 8, and R ¹ , R ² and R ³
Is a methyl group or an ethyl group.