JPH08295852A - Primer composition - Google Patents

Abstract

PURPOSE: To obtain a primer composition composed of a film-forming component, a polyisocyanate compound, a silane coupling agent, a halogen compound and an organic solvent, having excellent storage stability and free from gelling and deterioration troubles even by sealing a storage container after brief opening. CONSTITUTION: This primer composition contains (A) a film-forming component (preferably an acrylic resin having an acrylic acid ester and/or a methacrylic acid ester polymerized to the main chain or the side chain as a main monomer), (B) a polyisocyanate compound, (C) a silane coupling agent, (D) a halogen compound of formula R-CH2 -X (R is an aryl or vinyl; X is a halogen), (E) an organic solvent inert to isocyanate group and preferably further (F) a water-absorbing agent. The component D is preferably selected from allyl chloride, allyl bromide, α,α'-dibromo-p-xylene, cinnamyl chloride, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a primer composition which is excellent in storage stability and does not cause gelation even if the storage container is opened and then closed and stored to prevent deterioration over time.

[0002]

2. Description of the Related Art Sealing materials are used for bonding structures to each other or bonding metals to each other or metals to glass in a vehicle or the like. Usually, in order to improve the adhesiveness, the adherend is treated with a primer and then adhered with a sealing material.

Conventionally, as a primer used for such an application, a film-forming component, a polyisocyanate compound,
A composition containing a coupling agent, an organic solvent and the like is known. The polyisocyanate compound in this composition is a component that contributes to the adhesiveness, but it becomes a polymer due to the presence of water and the viscosity of the primer increases, so there was a problem in storage stability.

Therefore, in order to prevent the polymerization,
Conventionally, the water storage agent such as synthetic zeolite is contained in the primer composition, and the storage container is sealed to improve the storage stability.

[0005]

Conventionally, the primer composition is stabilized by means of the addition of the water absorbing agent and the blocking from the outside air as described above, and thereby the storage stability of the primer composition in the sealed state is improved. The sex has improved. But,
Once opened, the polyisocyanate compound polymerizes due to moisture in the air, so even if the storage container is closed and sealed after use, the polyisocyanate compound will polymerize after storing the used residue. However, it may be difficult to open and use it again.

The present invention has been made in view of the above facts, is excellent in storage stability, and even if the container of the storage container is opened and then closed and stored again, thickening or gelation occurs. Therefore, the present invention relates to a primer composition which can be used by re-storing the used residue.

[0007]

The primer composition of the present invention comprises (a) a film-forming component, (b) a polyisocyanate compound, (c) a silane coupling agent, and (d) the following general formula (A): ) A halogen compound represented by

[0008]

Embedded image

(E) An isocyanate group-inert organic solvent is contained. Further, in the primer composition of the present invention, as the film forming component, an acrylic resin in which an acrylic acid ester and / or a methacrylic acid ester is polymerized in a main chain or a side chain as a main monomer, or a methacrylic resin Resins are useful as membrane components.

Further, the primer composition preferably further contains a water absorbing agent.

Further, the halogen compound represented by the general formula (A) is an allyl chloride, allyl bromide, α, α'-dibromo-p-xylene, cinnamyl chloride, cinnamyl bromide, α, α'-dibromo. It is preferably selected from -m-xylene and α, α'-dibromo-o-xylene.

The present invention will be described in detail below. The film-forming component (a) used in the present invention is a polymer compound,
It has the following properties.

(1) It is soluble in an organic solvent. (2) When the organic solvent is volatilized from the organic solvent solution of the film forming component, the film forming component remains in the form of a film.

(3) It has no or very little active hydrogen. Among the above properties, (3) is that the isocyanate group or the Si—O bond portion in the compound compounded with the film forming component in the primer composition of the present invention and the film forming component do not react during storage. This is the property required for that.

The term "active hydrogen" as used herein refers to a reactive hydrogen atom that is bonded to an atom such as oxygen, sulfur or nitrogen in the molecule of an organic compound, and is a hydroxyl group, a mercapto group, an amino group or a carboxyl group. The hydrogen atom in etc. corresponds to this.

The film-forming component (a) used in the present invention includes
Urethane elastomer, chlorinated rubber, polycarbonate,
A wide range of polymer compounds such as polyvinyl chloride and acrylic resins are exemplified, but from the viewpoint of the appearance (transparency) of the primer, the film forming property, etc., the monomers whose main constituents are acrylic acid ester and / or methacrylic acid ester. An acrylic resin polymerized in the main chain or the side chain is preferably used as.

Examples of the acrylic resin include polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polyethyl methacrylate, poly n-propyl methacrylate, poly n-butyl methacrylate, methyl acrylate / methacrylic acid. Methyl acid copolymers, methyl methacrylate / butyl methacrylate copolymers and the like can be mentioned. Furthermore, acrylic acid, methacrylic acid, glycidyl acrylate, glycidyl methacrylate can be added to the acrylic ester and / or methacrylic acid ester monomers. The acrylic resin of the present invention also includes, for example, a methyl methacrylate / butyl methacrylate / methacrylic acid terpolymer copolymerized with an isoreactive monomer.

When the acrylic resin is used as a film component,
The primer has improved transparency and is preferable in appearance.

The polyisocyanate compound (b) used in the present invention refers to a compound having two or more isocyanate groups in the molecule.

In the present invention, various known compounds can be used, including a general-purpose polyisocyanate compound used for the production of ordinary polyurethane resins. For example,
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, phenylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-
Diisocyanate, naphthylene-1,5-diisocyanate and hydrogenated compounds thereof, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate,
Isophorone diisocyanate, 1-methyl-2,4-diisocyanate cyclohexane, 1-methyl-2,6-
Diisocyanate cyclohexane, dicyclohexylmethane diisocyanate, triphenylmethane triisocyanate and the like can be mentioned. Further, adducts using these compounds and trimethylolpropane, glycol, etc., isocyanurate modified products, carbodiimide modified products, alohanate modified products, burette modified products, etc. of these compounds can also be used. These polyisocyanate compounds may be used alone or in combination of two or more.

As the silane coupling agent (c), acrylic type, epoxy type, mercapto type and isocyanate type can be used, and epoxy type and isocyanate type are preferable from the viewpoint of effect.

Specific examples of these silane coupling agents include γ-glycidoxypropyltrimethoxysilane,
γ-glycidoxypropylmethyldimethoxysilane, 2
-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane,
γ-methacryloxypropylmethyldimethoxysilane,
γ-isocyanatopropyltrimethoxysilane and the like can be mentioned.

Among them, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane and the like are available. It is preferably used from the viewpoint of adhesiveness with the sealing material.

In the halogen compound represented by the following general formula (A) (d) of the present invention,

[0025]

Embedded image

In the formula, R represents an aryl group or a vinyl group, preferably an aryl group having 6 to 12 carbon atoms or a vinyl group having 2 to 10 carbon atoms. The aryl group and vinyl group may be unsubstituted or may have a substituent. The halogen atom of X is C
1, Br, F and I are mentioned, and a compound in which X is Cl and Br is preferably used.

Specifically, when R is an aryl group, examples of the halogen compound include benzyl chloride, benzyl bromide, chloromethylstyrene and αα'-dibromo-.
o-xylene, αα′-dibromo-m-xylene, αα
′ -Dibromo-p-xylene, αα′-dichloro-p-
Xylene is mentioned.

When R is a vinyl group, examples of the halogen compound include allyl bromide, allyl chloride, cinnamyl chloride, cinnamyl bromide and crotyl bromide.

From the viewpoint of industrial convenience, allyl bromide, allyl chloride and the like are preferable as the halogen compound used in the present invention. In addition to the halogen compound of the present invention, a halogen compound having two or more halogen atoms can be used in combination with the aryl group and vinyl group.

The organic solvent (e) used in the present invention is inert to the isocyanate group used in combination,
Further, those having an appropriate volatility are preferable.

Specifically, ethyl acetate, butyl acetate, cellosolve acetate, mineral spirits, toluene,
Examples include xylene, dimethylacetamide, methyl ethyl ketone, acetone, n-hexane, methylene chloride, tetrahydrofuran, and the like. Even if one kind is used alone,
You may mix and use 2 or more types.

It is preferable to use these organic solvents after drying or dehydrating them in order to prevent the influence of water on the isocyanate compound used together.

The primer composition of the present invention contains the above-mentioned components, and by additionally using a water-absorbing agent,
The water-absorbing agent takes in the water content in each ingredient and in the air,
As a result, the storage stability of the brimer composition of the present invention is further improved. Examples of the water absorbing agent include synthetic or natural zeolites, etc., as long as they do not affect the other components of the present invention such as the polyisocyanate compound,
A known water absorbing agent can be optionally used.

As the water absorbing agent, from the viewpoint of water absorbing ability, a zeolite type water absorbing agent such as synthetic or natural zeolite is preferable, and among them, those having a pore size of about 3 to 10 Å are preferably used. In addition, preferred specific examples of commercially available zeolites include Bayrit L powder manufactured by Bayer, molecular sieves manufactured by Union Carbide, and Zeolum manufactured by Tosoh.

The water absorbing agent may or may not be dissolved in the primer composition of the present invention, and if it is not dissolved, it may be allowed to coexist in the primer composition.

In order to further improve weather resistance and workability, the primer composition of the present invention may contain other components in addition to the above components. For example, inorganic pigments such as carbon black, lamp black, titanium white, red iron oxide, titanium yellow, zinc white, red lead, cobalt blue, iron black, aluminum powder, neozabon black RE, neo black RE, orazole black CN. , Orazol Black Ba (all manufactured by Ciba Geigy), organic dyes and pigments such as Spiron Blue 2BH (manufactured by Hodogaya Chemical Co., Ltd.), Cyasorb UV24Light A
bsorber, manufactured by American Cyanamid), Ubinul (Uvinul D-49, D-50, N-3)
5, N-539, manufactured by General Aniline Co., Ltd.) is effective in shielding or absorbing ultraviolet rays and visible rays, and improving the light resistance. In addition, it gives flexibility to primer coatings such as glass powder, clay, fillers such as molecular sieves (which also have water absorption capacity), thickeners, butylbenzyl phthalate, dioctyl phthalate, dibutyl phthalate, chlorinated paraffin, and adhesion. You may mix the plasticizer which improves strength.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples as long as the gist of the present invention is not exceeded.

[0038]

【Example】

(Comparative Example 1) In a 200 ml glass container, 4.0 g of chlorinated rubber (manufactured by Bayer, Pergut S20), 6.0 g of γ-glycidoxypropyltrimethoxysilane, polyisocyanate compound (D103 manufactured by Takeda Chemical Industries, Ltd.) 2
5.0 g and 64.0 g of ethyl acetate were added and mixed, and then 1 g of synthetic zeolite (synthetic zeolite Zeolum A-4, 8-10 mesh manufactured by Tosoh Corporation) was added to prepare a predetermined primer composition, and then glass. The container was sealed and left at 20 ° C. for 48 hours.

After that, the stopper was opened and left in an atmosphere of 20 ° C. × 55% RH for 30 minutes, then the stopper was closed again, and the properties of the primer composition stored in the dark at 20 ° C. were measured once a month. And the storage stability was evaluated. Also,
An aluminum plate as an adherend was tested for the adhesiveness of the primer composition after the preparation, which was stored in a tightly closed container, and the primer composition which was left open for one month and then plugged again and stored for 1 month.
As a sealing material, a polysulfide-based sealing material (Petam PS2000 manufactured by Bridgestone Corporation) was used according to JIS 5758. That is, a sample for an adhesiveness test was prepared, left for 7 days in an atmosphere of 20 ° C. and 55% RH, and then left in an oven at 50 ° C. for 7 days, and then the adhesiveness was evaluated. Here, CF ₁₀₀ is 100% of cohesive failure of the sealing material, and AF ₁₀₀ is 10% of interface failure.
Represents 0%. Interfacial failure is a failure that occurs at the interface between the sealing material and the adherend, occurs when the adhesive strength of the primer composition is insufficient, and cohesive failure of the sealing material, the adhesion is not destroyed at the interface, This refers to the phenomenon in which the sealing material breaks. The results are shown in Table 1.

Example 1 In the preparation of the primer composition of Comparative Example 1, except that 0.3 g of allyl bromide (Kanto Chemical Reagent) was added as a halogen compound represented by the chemical formula (A) of the present invention to the compounding ingredients. Prepared a primer composition in the same manner as in Comparative Example 1. The storage stability (observation of properties) of the obtained primer composition and the evaluation of the adhesiveness test are as follows.
The same procedure as in Comparative Example 1 was performed. The results are shown in Table 1. (Comparative Example 2) Acrylic resin (manufactured by Mitsubishi Rayon Co., Ltd., Dianal LR90) 20.0 in a 200 ml glass container.
g, γ-glycidoxypropyl trimexisilane 6.0
g, polyisocyanate compound (D1 manufactured by Takeda Pharmaceutical Co., Ltd.
03) 20.0 g and ethyl acetate 53 g are added and mixed,
Thereafter, 1 g of synthetic zeolite (synthetic zeolite Zeolum A-4 manufactured by Tosoh Corporation) was added to prepare a predetermined primer composition. Storage stability of the obtained primer composition,
The evaluation of the adhesiveness test was carried out in the same manner as in Comparative Example 1, but the one stored for one month after opening the cap was gelated, and the application for the adhesiveness test was impossible and the measurement could not be performed. Other results are shown in Table 2. (Comparative Example 3) A primer composition was prepared in the same manner as in Comparative Example 2 except that 0.5 g of 1-chlorobutane was added to the compounding ingredients of Comparative Example 2. The evaluation of the storage stability and the adhesion test of the obtained primer composition was carried out in the same manner as in Comparative Example 1,
What was stored for 1 month after opening the cap was gelled, and the application for the adhesiveness test was impossible and the measurement could not be performed. Other results are shown in Table 2. (Comparative Example 4) A primer composition was prepared in the same manner as in Comparative Example 2 except that 0.5 g of chlorobenzene was added to the compounding components of Comparative Example 2. The evaluation of the storage stability and the adhesiveness test of the obtained primer composition was carried out in the same manner as in Comparative Example 1, but the one preserved for 1 month after the opening was gelated and the application for the adhesiveness test was unsuccessful. It was possible and could not be measured. Other results are shown in Table 2. (Examples 2 to 5) As a halogen compound represented by the chemical formula (A) of the present invention, allyl bromide (0.5 g) in Example 2 and allyl bromide 1. 0 g, allyl chloride 1.0 g in Example 4, α,
A primer composition was prepared in the same manner as in Comparative Example 2 except that 1.0 g of α′-dibromo-p-xylene was added. The storage stability of the obtained primer composition and the adhesion test were evaluated in the same manner as in Comparative Example 1.

The results are shown in Table 2.

[0042]

[Table 1]

[0043]

[Table 2]

As is clear from Tables 1 and 2, a halogen compound containing only a film-forming component such as a chlorinated rubber or an acrylic resin, a polyisocyanate compound, a silane coupling agent and an organic solvent inert to the isocyanate group, The primer compositions not containing (Comparative Example 1 and Comparative Example 2) became unusable as a primer after opening for 1 month and after storage for 1 month due to thickening, decreased adhesiveness or gelation.

On the other hand, as in Examples 1 to 5 which are examples of the present invention, in the primer composition containing the halogen compound represented by the general formula (A), the kind and the addition amount of the film forming component and the halogen compound. Regardless of the fact, after opening the bottle, there is no change in state such as thickening even after storage for 2 months, and it can be used. Also, the adhesiveness test after storage for 1 month showed a decrease in adhesiveness. However, it was found that it has practical storage stability.

Further, when a halogen compound other than the general formula (A) of the present invention such as 1-chlorobutane or chlorobenzene was added, the effect of improving the storage stability as shown in Comparative Examples 3 and 4 was not obtained. Not shown, after opening the tube, gelation occurred after storage for 1 month, making it impossible to use as a primer.

[0047]

Since the primer composition of the present invention has the above-mentioned constitution, it has excellent storage stability, and does not cause thickening or gelation even when the storage container is opened and then closed and stored again. ,
Therefore, it showed an excellent effect that the residue after use could be stored again.

Claims (4)

[Claims] 1. A film-forming component, (b) a polyisocyanate compound, (c) a silane coupling agent, (d) a halogen compound represented by the following general formula (A), and (E) An isocyanate group-inert organic solvent, and a primer composition comprising: 2. The film-forming component is an acrylic resin in which an acrylic acid ester and / or a methacrylic acid ester is polymerized as a main monomer in a main chain or a side chain. The primer composition of. 3. The primer composition according to claim 1, further comprising a water absorbing agent in the primer composition. 4. The halogen compound represented by the general formula (A) is allyl chloride, allyl bromide, α,
α'-dibromo-p-xylene, cinnamyl chloride, cinnamyl bromide, α, α'-dibromo-m-
The primer composition according to claim 1, wherein the primer composition is selected from xylene and α, α′-dibromo-o-xylene.