JPH11343429A - Primer composition and adhesion method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having good adhesion to various kinds of substrates by compounding a saturated hydrocarbon-based polymer having one or more reactive silicon groups. SOLUTION: This primer composition contains (A) a saturated hydrocarbon- based polymer having at least one silicon-containing group which has a hydroxyl group or hydrolyzable group (for example, an alkoxy group) bound to a silicon atom and which can form a siloxane bond to cross-link the polymer, such as a hydrolyzable silyl group of the formula [R<1> and R<2> are each a 1-20C aryl, a 7-20C aralkyl or the like; X is OH or a hydrolyzable group; (a) is 0-3; (b) is 0-2; (m) is 0-19], preferably an isobutylene-based polymer or hydrogenated polybutadiene-based polymer having a number-average mol.wt. of 500-50,000. The primer composition preferably further contain (B) a silane coupling agent (for example, γ-aminopropyltrimethoxysilane) in an amount of 0.1-10,000 pts.wt. per 100 pts.wt. of the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a silicon-containing group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond (hereinafter referred to as "silicon-containing group").
It is called "reactive silicon group". The present invention relates to a primer composition containing a saturated hydrocarbon-based polymer having at least one) and an adhesion method.

[0002]

2. Description of the Related Art In recent years, elastic sealing materials have been widely used for buildings, motor vehicles, and the like. The sealing material is a material that is used to fill joints and gaps between various members to provide watertightness and airtightness.
Accordingly, various base materials constituting joints and around the window frame, that is, inorganic materials such as glass, ceramics, metal, cement, and mortar, and organic materials such as plastics (hereinafter, these are collectively referred to as “base materials”). ) Must have good adhesion. However, the adhesiveness of the sealing material itself is still insufficient, and the use of a primer is indispensable in many cases.

[0003] On the other hand, silicone-based, modified silicone-based, polysulfide-based and polyurethane-based sealants are well known as sealants applied to joints of the interior and exterior of general buildings. These sealing materials are used based on the concept of “the right place for the right material”, which uses the appropriate sealing material for each type of joint (including the type of base material). Is being developed.

As primers for building sealing materials, urethane-based primers containing isocyanate prepolymer as a main component, silane-based primers composed of silane-based low molecular weight compounds such as silane coupling agents, and organopolysiloxanes are commercially available. Have been. But,
Even if these primers are used, there is a problem that the effects of the primers cannot be exhibited for a long time because the weather resistance and water resistance of the adhesion are not sufficient.

On the other hand, a sealing material containing a saturated hydrocarbon polymer containing a reactive silicon group as a main component (particularly, an isobutylene-based sealing material having an isobutylene-based polymer as a main chain skeleton) has recently been developed. This isobutylene-based sealing material has characteristics such as dynamic followability, heat resistance, weather resistance, water resistance, excellent paintability, and does not contaminate the periphery of joints, and has the performance as a universal sealing material. No primer for isobutylene sealant has been developed.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a primer composition having good adhesion to various substrates, and in particular, to a saturated hydrocarbon polymer having at least one reactive silicon group. It is an object of the present invention to provide a primer composition and a bonding method for satisfactorily bonding a sealing material as a main component and various substrates.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve such problems, and as a result, have found that a saturated hydrocarbon polymer (A) having at least one reactive silicon group can be obtained.
It has been found that the object can be achieved by a primer composition containing the present invention, and the present invention has been completed. That is,
The present invention comprises, as the component (A), a saturated hydrocarbon polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having at least one silicon-containing group capable of crosslinking by forming a siloxane bond. It relates to a primer composition characterized by the fact that, in particular,
(A) 100 parts by weight of a saturated hydrocarbon polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom as a component and having at least one silicon-containing group capable of crosslinking by forming a siloxane bond. A primer composition comprising 0.1 to 10000 parts by weight of a silane coupling agent as component (B).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The saturated hydrocarbon polymer having at least one reactive silicon group of the component (A) used in the present invention is a component that is a feature of the present invention, and has good adhesion to various substrates such as glass and metal. It functions as a component for forming a film having excellent weather resistance and water resistance through glass.
That is, it is a component that imparts strong adhesion and durability to the primer composition of the present specification.

The saturated hydrocarbon polymer having at least one reactive silicon group as the component (A) is a polymer substantially containing no carbon-carbon unsaturated bond other than an aromatic ring. , Polypropylene, polyisobutylene, hydrogenated polybutadiene, hydrogenated polyisoprene, and the like. As the reactive silicon group,
General formula (1),

[0010]

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(Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
To 20 aryl groups, aralkyl groups having 7 to 20 carbon atoms or (R ′) ₃ SiO— (R ′) are each independently a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. ) Is a triorganosiloxy group. X is each independently a hydroxyl group or a hydrolyzable group. Further, a is 0, 1, 2, or 3, b is 0, 1, or 2, and a and b do not become 0 at the same time. M is 0 or 1 to 1
Which is an integer of 19).

Examples of the hydrolyzable group include groups generally used such as 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. Can be Among these, an alkoxy group, an amide group and an aminooxy group are preferred, but an alkoxy group is particularly preferred because of its mild hydrolyzability and easy handling.

A hydrolyzable group or a hydroxyl group can be bonded to one silicon atom in the range of 1 to 3 and (a + Σ
b) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different. The number of silicon atoms forming the reactive silicon group is one or more. In the case of silicon atoms linked by a siloxane bond or the like, the number is preferably 20 or less.

In particular, the general formula (2)

[0015]

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(Wherein R ² , X and a are as defined above) are preferred because they are easily available. The number of reactive silicon groups in one molecule of the saturated hydrocarbon polymer of the component (A) is one or more, preferably 1.1 to 5. If the number of reactive silicon groups contained in the molecule is less than one, the curability becomes insufficient and a good film may not be obtained.

The reactive silicon group may be present at the terminal or inside the molecular chain of the saturated hydrocarbon polymer of the component (A), or may be present at both. In particular, when the reactive silicon group is at the molecular end, the effective network chain amount of the saturated hydrocarbon polymer component (A) contained in the finally formed cured film is increased, so that the high strength This is preferable in that a coating can be easily obtained.

These (A) saturated hydrocarbon polymers having at least one reactive silicon group can be used alone or in combination of two or more. The polymer constituting the skeleton of the saturated hydrocarbon polymer having at least one reactive silicon group as the component (A) used in the present invention includes (1) a carbon atom having one carbon atom such as ethylene, propylene, 1-butene and isobutylene. To 6 as the main monomer, (2) homopolymerization of a diene compound such as butadiene, isoprene, or the like, or hydrogenation after copolymerization with the olefin compound. However, the isobutylene-based polymer and the hydrogenated polybutadiene-based polymer can easily introduce a functional group into a terminal, easily control a molecular weight, and can increase the number of terminal functional groups. It is preferred.

In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units,
The monomer unit having a copolymer with isobutylene is contained in the isobutylene-based polymer in an amount of preferably 50% or less (% by weight, the same applies hereinafter), more preferably 30% or less, particularly preferably 10% or less. Is also good. Examples of such monomer components include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, allyl silanes, and the like. Such copolymer components include, for example, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene,
Vinylcyclohexene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, β-pinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyl Trimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, allyltrichlorosilane, allylmethyldichlorosilane, Allyldimethylchlorosilane, allyldimethylmethoxysilane, allyltrimethylsilane,
Diallyldichlorosilane, diallyldimethoxysilane,
Diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and the like.

When vinylsilanes or allylsilanes are used as monomers copolymerizable with isobutylene, the content of silicon increases and the number of groups that can act as a silane coupling agent increases. Is improved in adhesiveness. In the hydrogenated polybutadiene-based polymer and other saturated hydrocarbon-based polymers, as in the case of the isobutylene-based polymer, other monomer units are contained in addition to the main monomer unit. You may.

The saturated hydrocarbon polymer having at least one reactive silicon group as the component (A) used in the present invention includes butadiene, butadiene and the like as long as the object of the present invention is achieved.
A small amount, preferably 10% or less, more preferably 5% or less, particularly 1% or less, of a monomer unit such as a polyene compound such as isoprene which has a double bond after polymerization may be contained. As the saturated hydrocarbon polymer having at least one reactive silicon group as the component (A), the number average molecular weight of an isobutylene polymer or a hydrogenated polybutadiene polymer is preferably about 500 to 50,000. And those having a liquid or fluidity of about 1,000 to 20,000 are preferred from the viewpoint of easy handling.

Next, the process for producing a saturated hydrocarbon polymer having at least one reactive silicon group as the component (A) will be described with reference to an isobutylene polymer having a reactive silicon group. Among the isobutylene-based polymers having at least one reactive silicon group, the isobutylene-based polymer having a reactive silicon group at a molecular chain terminal is a polymerization method called an inifer method (using both an initiator called an inifer and a chain transfer agent). End-functional type, preferably an all-terminal-functional isobutylene-based polymer obtained by a cationic polymerization method using a specific compound.
For example, the dehydrohalogenation reaction of this polymer and
After obtaining a polyisobutylene having an unsaturated group at a terminal by a reaction of introducing an unsaturated group into a polymer as described in JP-A-3-105005, the general formula

[0023]

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(Wherein R ¹ , R ² , X, a, b and m
Is the same as above. ) (This compound is a compound in which a hydrogen atom is bonded to a group represented by the general formula (1)), preferably a general formula

[0025]

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(Wherein, R ² , X and a are the same as described above) to form a reactive silicon group by performing an addition reaction called hydrosilylation reaction using a platinum catalyst. There is a method of introducing into the coalescence. Examples of the hydrosilane compound include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; and trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, and phenyldimethoxysilane. Alkoxysilanes; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; and ketoximesilanes such as bis (dimethylketoxime) methylsilane and bis (cyclohexylketoxime) methylsilane. However, the present invention is not limited to these. Of these, halogenated silanes and alkoxysilanes are particularly preferred.

Such a manufacturing method is described in, for example,
-69659, JP-B-7-108928, JP-A-251468, JP-A-64-22904, and JP-A-2539445. Further, the isobutylene-based polymer having a reactive silicon group in the molecular chain is produced by adding a vinylsilane or an allylsilane having a reactive silicon group to a monomer mainly composed of isobutylene and copolymerizing the monomer.

Further, in the polymerization for producing an isobutylene-based polymer having a reactive silicon group at the terminal of the molecular chain, a vinylsilane or allylsilane having a reactive silicon group other than the main component isobutylene monomer is copolymerized. After that, by introducing a reactive silicon group to the terminal, an isobutylene-based polymer having a reactive silicon group at the terminal and in the molecular chain is produced.

Examples of vinylsilanes and allylsilanes having a reactive silicon group include vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, divinyldichlorosilane, divinyldimethoxysilane, allyltrichlorosilane, and allylsilane. Examples include methyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, diallyldichlorosilane, diallyldimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropylmethyldimethoxysilane.

The hydrogenated polybutadiene-based polymer is, for example,
For example, first, a hydroxy-terminated polybutadiene-based polymer
Hydroxyl groups of the body to oxymetal groups such as -ONa and -OK
After that, the general formula (3): CH_Two = CH-R^Three —Y (3) (where Y is a halogen atom such as a chlorine atom or an iodine atom)
Child, R^Three Is -R^Four -, -R ^Four -OCO- or -R^Four −
CO- (R^Four Is a divalent hydrocarbon group having 1 to 20 carbon atoms,
Alkylene group, cycloalkylene group, arylene group,
A aralkylene group is preferred),
-CH_Two -, -R "-C₆ H_Five -CH_Two -(R "is carbon
Divalent groups selected from (hydrocarbon groups of formulas 1 to 10)
The organic halogen compound represented by
Hydrogenated polybuta having terminal olefin groups
Diene-based polymer (hereinafter referred to as terminal olefin hydrogenated polybutadi
(Also referred to as an ene-based polymer).

A method for converting a terminal hydroxyl group of a terminally hydrogenated polybutadiene polymer into an oxymetal group is as follows.
Alkali metals such as Na and K; metal hydrides such as NaH; metal alkoxides such as NaOCH ₃ ;
A method of reacting with an alkali hydroxide such as OH and KOH is exemplified. In the above-mentioned method, a terminal olefin hydrogenated polybutadiene polymer having almost the same molecular weight as the terminal hydroxy hydrogenated polybutadiene polymer used as a starting material can be obtained. Before reacting the organic halogen compound of the formula (3), a polyvalent organic halogen compound containing two or more halogens in one molecule such as methylene chloride, bis (chloromethyl) benzene, bis (chloromethyl) ether, etc. If the reaction is carried out, the molecular weight can be increased. Then, if the reaction is carried out with the organic halogen compound represented by the general formula (3), a hydrogenated polybutadiene polymer having a higher molecular weight and having an olefin group at the terminal can be obtained. Can be.

Specific examples of the organic halogen compound represented by the general formula (3) include, for example, allyl chloride,
Allyl bromide, vinyl (chloromethyl) benzene,
Allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl (chloromethyl) ether, allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy)
Examples include, but are not limited to, benzene and allyloxy (chloromethyl) benzene. Of these, allyl chloride is preferable because it is inexpensive and easily reacts.

The introduction of the reactive silicon group into the hydrogenated polybutadiene polymer at the terminal olefin is carried out by using a platinum catalyst as in the case of the isobutylene polymer having a reactive silicon group at the molecular chain end. It is produced by performing an addition reaction. As described above, when the saturated hydrocarbon polymer having a reactive silicon group does not substantially contain an unsaturated bond which is not an aromatic ring in the molecule, an organic polymer having an unsaturated bond or an oxyalkylene-based polymer may be used. Compared to a film formed from a conventional rubber-based polymer such as a polymer, the weather resistance is significantly improved. Also, since the polymer is a hydrocarbon polymer, it has good moisture barrier properties and water resistance,
It has excellent adhesion performance to various inorganic base materials such as glass and aluminum, and forms a film with high moisture barrier properties.

The content of the saturated hydrocarbon polymer having at least one reactive silicon group as the component (A) in the primer composition of the present invention is preferably 1% or more, more preferably 3% or more, and more preferably 5%. The above is particularly preferred. In particular, when the primer composition of the present invention is used for a porous substrate such as mortar, it is necessary to further increase the film thickness of the coating in order to prevent leaching of moisture from the porous substrate. The combined content is preferably 5% or more, more preferably 10% or more, and particularly preferably 20% or more.

The component (A), a saturated hydrocarbon polymer having at least one reactive silicon group, has a high viscosity and poor workability. Therefore, for the purpose of lowering the viscosity of the polymer and improving the handling, various plasticizers may be added to such an extent that the adhesiveness and stainability of the primer composition of the present invention are not deteriorated. Examples of the plasticizer having good compatibility with the saturated hydrocarbon polymer as the component (A) of the present invention include polyvinyl oligomers such as polybutene, hydrogenated polybutene, hydrogenated α-olefin oligomer, and atactic polypropylene; biphenyl, Aromatic oligomers such as triphenyl; hydrogenated polyene oligomers such as hydrogenated liquid polybutadiene; paraffin oligomers such as paraffin oil and chlorinated paraffin oil; cycloparaffin oligomers such as naphthene oil.

In addition, phthalate ester plasticizers, non-aromatic dibasic ester plasticizers, phosphate ester plasticizers, etc. do not lower the adhesiveness, weather resistance, heat resistance, etc. of the primer composition of the present invention. To the extent, it may be used in combination with the above-mentioned plasticizer. These may be used alone or in combination of two or more. When the plasticizer introduces a reactive silicon group into the saturated hydrocarbon polymer, the reaction temperature is adjusted,
It may be used in place of the solvent for the purpose of adjusting the viscosity of the reaction system.

The amount of the plasticizer is preferably 1 to 100 parts based on 100 parts (parts by weight, hereinafter the same) of a saturated hydrocarbon polymer having at least one reactive silicon group as the component (A). 10 to 50 parts are more preferred. If the amount of the plasticizer is below this range, the plasticizing effect is small, and
If it exceeds this range, sufficient adhesiveness may not be obtained. The silane coupling agent of the component (B) of the present invention comprises:
(A) A tough film is formed by, for example, reaction with a saturated hydrocarbon polymer having at least one reactive silicon group as a component, and various base materials such as glass, metal, and mortar and an isobutylene-based sealing material or a modified material are used. This is to improve the adhesive strength with various sealing materials such as silicone-based sealing materials. The silane coupling agent of the component (B) is a compound having a group containing a silicon atom to which a hydrolyzable group is bonded (hereinafter referred to as a hydrolyzable silicon group) and a functional group other than the group. Examples of the hydrolyzable silicon group include those in which X in the group represented by the general formula (1) is a hydrolyzable group. Specifically, the groups already exemplified as the hydrolyzable group can be mentioned, but a methoxy group, an ethoxy group and the like are preferable from the viewpoint of the hydrolysis rate. The number of hydrolyzable groups is preferably 2 or more, particularly preferably 3 or more.

Examples of the functional group other than the hydrolyzable silicon group include primary, secondary, and tertiary amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurates, and halogens. . Of these, primary, secondary, and tertiary amino groups, epoxy groups, isocyanate groups, isocyanurates, and the like are preferable, and isocyanate groups and amino groups are particularly preferable.

Specific examples of the silane coupling agent (B) include γ-aminopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyl Dimethoxysilane, γ- (2
-Aminoethyl) aminopropyltriethoxysilane,
γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinyl Amino group-containing silanes such as benzyl-γ-aminopropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, etc. Mercapto group-containing silanes; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Methoxysilane, beta-
Epoxy group-containing silanes such as (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β-
Carboxysilanes such as (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-
Vinyl-type unsaturated group-containing silanes such as methacryloyloxypropylmethyldimethoxysilane and γ-acroyloxypropylmethyltriethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; tris (trimethoxysilyl) isocyanurate Isocyanurate silanes such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane and the like. Can be. In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated amino silane complexes, blocked isocyanate silanes, phenylamino long-chain alkyl silanes, amino silylated silicones, silylated polyesters, and the like, which are modified derivatives thereof, are also used as silane coupling agents. Can be used.

The silane coupling agent of the component (B) used in the present invention is added in an amount of 0.1 to 100 parts of the saturated hydrocarbon polymer having at least one reactive silicon group of the component (A).
Used in the range of 1 to 10000 parts. In particular, 1 to 10
It is preferable to use it in the range of 0 parts. The silane coupling agent of the component (B) may be used alone or in combination of two or more. In the primer composition of the present invention, an adhesiveness-imparting agent other than the silane coupling agent as the component (B) can be used.

The organic titanate which is the component (C) of the present invention can improve the adhesive strength between various base materials such as glass, metal and mortar and various sealing materials such as isobutylene-based sealing material and modified silicone-based sealing material. It is a component that improves. It also has the function of improving the adhesiveness at the joint surface when the sealing material is spliced. In particular, the sealing material other than the silicone sealing material is used for the silicone sealing material (first-time sealing material). It has the function of improving the adhesiveness of the joint surface when joining. further,
The organic titanates of the component (C) are formed by a condensation reaction of the reactive silicon group of the silane coupling agent of the component (B) with the saturated hydrocarbon polymer having at least one reactive silicon group of the component (A). It is a component that also functions as a silanol condensation catalyst that promotes

The organic titanates of the component (C) include organic titanates, chelate compounds of titanium, chelate compounds of silicates of titanium, titanate coupling agents, and partially hydrolyzed condensates thereof. No. Specific examples of organic titanates include tetraisopropyl titanate, tetra-normal butyl titanate, butyl titanate dimer,
Tetrakis (2-ethylhexyl) titanate, tetrastearyl titanate, tetramethyl titanate, diethoxybis (acetylacetonato) titanium, diisopropylbis (acetylacetonato) titanium, diisopropoxybis (ethylacetoacetate) titanium, isopropoxy (2-ethyl) -1,3-hexanediolato) titanium, di (2-ethylhexoxy) bis (2-ethyl-
Examples thereof include 1,3-hexanediolato) titanium, di-n-butoxybis (triethanolaminato) titanium, titanium tetraacetylacetonate, hydroxybis (lactato) titanium, and hydrolyzed condensates thereof. Further, as a specific example of a titanate-based coupling agent,

[0043]

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And the hydrolytic condensates thereof. (C) used in the present invention
The organic titanates of the component are used in the range of 0.1 to 10,000 parts based on 100 parts of the saturated hydrocarbon polymer having at least one reactive silicon group of the component (A). In particular, it is preferable to use in the range of 1 to 100 parts. The organic titanates of the component (C) may be used alone or in combination of two or more.

In the primer composition of the present invention,
As the component (D), a silanol condensation catalyst can be used as a component having a function of curing the primer composition of the present invention to give air drying properties. Examples of the silanol condensation catalyst of the component (D) include divalent and tetravalent tin-based curing catalysts, aluminum-based curing catalysts, and amine-based curing catalysts. Among these, a tetravalent tin-based curing catalyst is preferable because of its high catalytic activity. Tetravalent Examples of tin curing catalyst include tin carboxylates, dialkyl tin oxides, and the general formula _{(4), Q d Sn (} OZ) 4-d, or [Q ₂ Sn (OZ)] ₂ O (4) (wherein Q is a monovalent hydrocarbon group having 1 to 20 carbon atoms,
Is a monovalent hydrocarbon group having 1 to 20 carbon atoms or S
represents an organic group having a functional group capable of forming a coordination bond with n. Further, d is 0, 1, 2, or 3. And the like. Further, a tetravalent tin compound such as dialkyltin oxide or dialkyltin diacetate and a low molecular weight silicon compound having a hydrolyzable silicon group such as tetraethoxysilane, methyltriethoxysilane, diphenyldimethoxysilane, or phenyltrimethoxysilane The reactants are also effective as curing catalysts that significantly accelerate the silanol condensation reaction. Among these, the compound represented by the general formula (4), that is, a chelate compound such as dibutyltin bisacetylacetonate or a tin alcoholate has a high activity as a silanol condensation catalyst, and the film formation rate of the primer composition is increased. It is more preferable.

Specific examples of the tin carboxylate include:
For example, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethyl malate, dibutyltin diethylmalate, dibutyltin dibutylmalate, dibutyltin diisooctylmalate, dibutyltin dibutyltin Examples include tridecyl malate, dibutyl tin dibenzyl malate, dibutyl tin maleate, dioctyl tin diacetate, dioctyl tin distearate, dioctyl tin dilaurate, dioctyl tin diethyl malate, dioctyl tin diisooctyl malate, and the like.

Specific examples of the dialkyltin oxides include dibutyltin oxide, dioctyltin oxide, and a mixture of dibutyltin oxide and phthalic acid ester. Specific examples of the chelate compound include:

[0048]

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[0049] However, the present invention is not limited thereto. Of these, dibutyltin bisacetylacetonate is most preferred because of its high catalytic activity, low cost, and easy availability. Specific examples of the tin alcoholates include:

[0050]

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[0051] However, the present invention is not limited thereto. Of these, dialkyltin dialkoxides are preferred. In particular, dibutyltin dimethoxide is
It is more preferable because of low cost and easy availability. Further, a silanol condensation catalyst other than the above-mentioned tetravalent tin-based curing catalyst may be used. Specifically, a divalent tin-based curing catalyst such as tin octylate; an aluminum-based curing catalyst such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetylacetonate; Lead octylate; butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine,
Xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole,
1,8-diazabicyclo (5,4,0) undecene-7
Amine-based curing catalysts such as (DBU) or salts of these amine-based compounds with carboxylic acids, etc .; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction formation between excess polyamines and epoxy compounds Object; γ-
Silanol condensation catalysts such as silane coupling agents having an amino group such as aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane; and other known catalysts such as other acidic catalysts and basic catalysts. Examples thereof include a silanol condensation catalyst. These catalysts may be used alone or in combination of two or more.

The compounding amount of the silanol condensation catalyst of the component (D) is 0.1 to 100 parts per 100 parts of the saturated hydrocarbon polymer having at least one reactive silicon group of the component (A).
About 100 parts are preferable, and 1 to 20 parts is more preferable.
When the amount of the silanol curing catalyst (D) is less than this range, the film formation speed may be slow, and the film may not be sufficiently formed. On the other hand, when the amount of the silanol curing catalyst (D) exceeds this range, the open time becomes too short, which is not preferable from the viewpoint of workability.

In the present invention, a solvent can be used to adjust the viscosity of the primer composition to a value suitable for the primer coating operation. The solvent is the component (A) of the present invention.
Any type can be used as long as it can dissolve the component (D), and the type is not particularly limited. Specific examples of such a solvent include hydrocarbon solvents such as toluene, xylene, heptane, hexane, petroleum solvents, halogen solvents such as trichloroethylene, ester solvents such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, and methyl isobutyl. Examples thereof include ketone solvents such as ketones, alcohol solvents such as methanol, ethanol and isopropanol, and silicone solvents such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. These solvents may be used alone or in combination of two or more.

The amount of the solvent is preferably about 100 to 10000 parts, more preferably 200 to 2000 parts, per 100 parts of the saturated hydrocarbon polymer having at least one reactive silicon group as the component (A). . If the amount of the solvent is less than this range, the viscosity of the primer composition becomes too high, which is not preferable from the viewpoint of workability. If the amount of the solvent exceeds this range, sufficient adhesiveness may not be obtained.

In the primer composition of the present invention, various antioxidants are used as required. Such antioxidants include phenolic antioxidants, aromatic amine antioxidants, sulfur hydroperoxide decomposers, phosphorus hydroperoxide decomposers, benzotriazole UV absorbers, salicylate UV absorbers, benzophenone based Examples include an ultraviolet absorber, a hindered amine light stabilizer, and a nickel light stabilizer.

Specific examples of the phenolic antioxidant include 2,6-di-t-butylphenol, 2,4-di-t-butylphenol, and 2,6-di-t-butyl-4.
-Methylphenol, 2,5-di-t-butylhydroquinone, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate],
2,2′-methylenebis (4-methyl-6-t-butylphenol), 4,4′-butylidenebis (3-methyl-6-t-butylphenol), 4,4′-thiobis (3-methyl-6-t -Butylphenol) and the like.

Specific examples of the aromatic amine antioxidant include N, N'-diphenyl-p-0-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,
Examples thereof include 2-dihydroquinoline. Specific examples of the sulfur-based hydroperoxide decomposer include dilauryl-
3,3'-thiodipropionate, ditridecyl-3,
3'-thiodipropionate, distearyl-3,3 '
-Thiodipropionate and the like.

Specific examples of the phosphorus hydroperoxide decomposer include diphenylisooctyl phosphite,
Examples include triphenyl phosphite. Specific examples of the benzotriazole-based ultraviolet absorber include 2-
(3,5-di-t-butyl-2-hydroxyphenyl)
-5-chlorobenzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) Benzotriazole, 2-
(5-methyl-2-hydroxyphenyl) benzotriazole and the like can be exemplified.

Specific examples of the salicylate-based ultraviolet absorber include 4-t-butylphenyl salicylate,
Examples thereof include 4-di-t-butylphenyl-3,5′-di-t-butyl-4′-hydroxybenzoate. Specific examples of the benzophenone-based ultraviolet absorber,
2,4-dihydroxybenzophenone, 2-hydroxy-
4-methoxybenzophenone, 2-hydroxy-4-n-
Octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone and the like can be exemplified.

Specific examples of the hindered amine light stabilizer include bis (2,2,6,6-tetramethyl-4
-Piperidyl) sebacate, bis (1,2,2,6,
6, -pentamethyl-4-piperidyl) sebacate, 1
-{2- [3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl} -4-
[3- (3,5-Di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,
6,6, -tetramethylpiperidine and the like can be exemplified.

Specific examples of the nickel-based light stabilizer include nickel dibutyldithiocarbamate, [2,2 ′
-Thiobis (4-t-octylphenolate)]-2-
Ethylhexylamine nickel (II), [2,2'-
Thiobis (4-t-octylphenolate)]-n-butylamine nickel (II) and the like. These antioxidants may be used alone or in combination of two or more. It may work more effectively when used in combination than when used alone. In particular, the combination of a phenolic antioxidant, a salicylate ultraviolet absorber and a hindered amine light stabilizer remarkably improves the weather resistance of a saturated hydrocarbon polymer having at least one reactive silicon group as the component (A). It is more preferable to improve
The amount of the antioxidant is preferably about 0.1 to 20 parts, more preferably 1 to 10 parts, per 100 parts of the component (A). If the amount is less than 0.1 part, the effect of improving the weather resistance may not be sufficient. If the amount is more than 20 parts, the cost and adhesiveness of the primer composition deteriorate.

Further, the primer composition of the present invention includes:
In order to further improve the weathering adhesion, a weathering adhesion improver (a compound or a photopolymerizable substance having an unsaturated group in the molecule that causes polymerization by reacting with oxygen in the air) is added as necessary. You. These are effective when used alone, and may be used in combination. The compound having an unsaturated group in the molecule which causes polymerization by reacting with oxygen in the air, that is, an oxidative polymerization reactive substance. Specific examples of the oxidative polymerization reactive substance include an ester compound of an unsaturated higher fatty acid and an alcohol, 1,2-polybutadiene,
1,4-polybutadiene, diene polymers and copolymers, such as C ₅ -C ₈ dienes, further various modified products of the polymer or copolymer (maleated modified product, boiled oil modification products, etc.)
and so on.

Specific examples of the above ester compounds of unsaturated higher fatty acids include oleic acid, linoleic acid, linolenic acid, eleostearic acid, ricanic acid, ricinoleic acid,
Higher unsaturated fatty acids such as arachidonic acid, methanol,
Bound to a monohydric alcohol such as ethanol, a dihydric alcohol such as ethylene glycol or propylene glycol, a trihydric alcohol such as trimethylolpropane or glycerin, a tetrahydric alcohol such as pentaerythritol, a hexahydric alcohol such as sorbide, or a silicon atom. There is an ester compound obtained by a condensation reaction with an alcohol selected from an organic silicon compound having a hydroxyl group via an organic group.

Among these ester compounds, linseed oil, tung oil, soybean oil, and the like containing triglycerin ester which is an ester of unsaturated higher fatty acid and glycerin as a main component,
Asa seed oil, isano oil, urushi kernel oil, perilla oil, Eucommia oil, Kaya oil, walnut oil, poppy oil, cherry seed oil,
Drying oils such as pomegranate seed oil, safflower oil, tobacco seed oil, goose kernel oil, rubber seed oil, sunflower seed oil, grape kernel oil, balsam seed oil, and honeysuckle seed oil are inexpensive,
It is more preferable because it can be easily obtained.

Among the above-mentioned drying oils, tung oil, eutherzica oil, pomegranate seed oil, mainly containing triglycerin esters of conjugated unsaturated higher fatty acids such as eleostearic acid, ricanoic acid, punicic acid and cannulpic acid, Balsam seed oil and the like are more preferred because of their high weather resistance improving effect. The compound having an unsaturated group in the molecule which causes polymerization by reacting with oxygen in the air may be used alone or in combination of two or more.

The above-mentioned photopolymerizable substance is a compound having an unsaturated group that causes a polymerization reaction when a double bond in a molecule is activated by irradiation with light. Representative examples of the photopolymerizable unsaturated group contained in the photopolymerizable substance include a vinyl group, an allyl group, a vinyl ether group, a vinyl thioether group, a vinyl amino group, an acetylenically unsaturated group, an acryloyl group, a methacryloyl group, Styryl group, cinnamoyl group and the like,
Among these, an acryloyl group or a methacryloyl group is preferable because of its high photoinitiation efficiency.

Examples of the photopolymerizable substance having an acryloyl group or a methacryloyl group as a photosensitive group include acrylamide derivatives, methacrylamide derivatives, (meth) acrylates, and among them, (meth) acrylate However, it is more preferable because there are many types and it is easily available. In this specification, (meth) acrylate is a general term for acrylate and methacrylate.

Specific examples of the above (meth) acrylate include propylene (or butylene,
Ethylene) glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate having three functional groups, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate having four or more functional groups, dipentaerythritol Examples thereof include penta and hexa (meth) acrylate. Specific examples of the oligomer include a polyethylene glycol di (meth) acrylate and a polypropylene glycol di (meth) acrylate having a molecular weight of 10 or less.
000 or less oligoesters. 1
The number of acrylic or methacrylic unsaturated groups in the molecule is
Two or more are preferable, and three or more are more preferable. The effect of improving the weather resistance and adhesion of the unsaturated acrylic compound increases as the number of functional groups increases.

The photopolymerizable substance may be used alone,
Two or more kinds may be used in combination. The amount of the weathering adhesion improver to be added is preferably about 0.1 to 100 parts, more preferably 1 to 20 parts, per 100 parts of the component (A). The blending amount is 0.
If the amount is less than 1 part, the effect of improving the weather resistance may not be sufficient, and if it exceeds 100 parts, the storage stability of the primer composition may decrease.

In the primer composition of the present invention, various fillers are used as needed. Specific examples of the filler include, for example, wood powder, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut husk powder, rice husk powder, graphite, diatomaceous earth, clay, fumed silica, precipitated silica , Silicic anhydride, carbon black, calcium carbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, aluminum fine powder, flint powder,
Zinc powder and the like. Among these fillers, precipitated silica, fumed silica, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable. These fillers may be used alone or in combination of two or more. When the filler is used, the amount is preferably from 1 to 500 parts, more preferably from 50 to 200 parts, per 100 parts of the component (A).

In addition to the components (A) to (D) and the above-mentioned plasticizers, solvents, antioxidants, weathering adhesion improvers and fillers, the primer composition of the present invention may optionally contain Various additives are added. Examples of such additives include, for example, a physical property adjuster for adjusting the tensile properties of the resulting cured film, a storage stability improver, a radical inhibitor, a metal deactivator, an ozone deterioration inhibitor, and an anti-sagging agent. , Lubricant,
Pigments, foaming agents and the like. Specific examples of such additives include, for example, Japanese Patent Publication No. 4-69659 and Japanese Patent Publication No.
-1088928, Japanese Patent Publication No. 251468, and Japanese Patent Application Laid-Open No. Sho 64-22904.

The method of bonding a sealing material to a substrate using the primer composition of the present invention can be carried out, for example, by the following procedure. First, the primer composition of the present invention is applied on a washed substrate, and left under a condition corresponding to the primer composition to form a film. Subsequently, the prepared sealing material can be applied on the primer layer on which the film has been formed, and cured in an oven.

The sealing material applied on the primer layer in the present invention includes modified silicone, silicone, polyurethane, acrylurethane, polysulfide, modified polysulfide, butyl rubber, acrylic, SBR, fluorine-containing. Sealing materials, such as
Oily caulk, silicone mastic, and
A sealing material mainly containing a saturated hydrocarbon polymer having a reactive silicon group can be used. Among these, the primer composition of the present invention is effective when used as a sealing material containing a saturated hydrocarbon-based polymer having a reactive silicon group as a main component, and in particular, an isobutylene-based polymer having a reactive silicon group. When applied to a sealing material mainly composed of a coalescence (for example, an isobutylene-based sealing material disclosed in Japanese Patent Publication No. 4-69659), it is preferable because of good adhesiveness.

The primer composition of the present invention comprises various metals such as iron, stainless steel, aluminum, nickel, zinc, and copper, acrylic resin, phenol resin, epoxy resin, polycarbonate resin, polybutylene terephthalate resin, and alkali-treated fluorine. Synthetic resin materials such as resin, inorganic materials such as glass, ceramic, cement, mortar, and modified silicone, silicone,
Various types of sealing materials can be firmly bonded to polyurethane-based, acrylic urethane-based, polysulfide-based, modified polysulfide-based, butyl rubber-based, acrylic-based, SBR-based, fluorine-containing, and isobutylene-based sealing materials and various types of sealing materials.

The primer composition of the present invention can be coated on a substrate by a commonly used coating method, for example, a brush coating method, a spray coating method, a wire bar method, a blade method, a roll coating method, a dipping method and the like. The primer composition of the present invention can generally form a film at normal temperature, but the film may be formed under various temperature conditions in order to adjust the film formation speed.

[0076]

EXAMPLES Next, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Production Example 1 A three-way cock was attached to a 2 L pressure-resistant glass container, and the inside of the container was purged with nitrogen. Then, the container was dried using ethyl syringe by allowing it to stand for one night or more with ethylcyclohexane (molecular sieves 3A). 138m
l and toluene (dried by allowing to stand over one night with Molecular Sieves 3A) 1012
ml, p-DCC (the following compound) 8.14 g (35.2
mmol).

[0078]

Embedded image

Next, 254 ml of isobutylene monomer
(2.99 mol) of a pressure-resistant glass liquefaction sampling tube with a needle valve was connected to a three-way cock, and the polymerization vessel was cooled by placing it in a -70 ° C dry ice / ethanol bath, and then using a vacuum pump. To reduce the pressure inside the container. After opening the needle valve and introducing the isobutylene monomer from the liquefied gas collecting tube into the polymerization vessel, the inside of the vessel was returned to normal pressure by introducing nitrogen from one of the three-way cocks. Next, 0.387 g of 2-methylpyridine (4.
15 mmol) was added. Next, 4.90 titanium tetrachloride
The polymerization was initiated by adding 4 ml (44.7 mmol). After a reaction time of 70 minutes, 9.65 g of allyltrimethylsilane
(13.4 mmol) was added, and an allyl group was introduced into the polymer terminal. After a reaction time of 120 minutes, the reaction solution was washed four times with 200 ml of water, and then the solvent was distilled off to obtain an allyl-terminated isobutylene polymer.

Then, 200 g of the allyl-terminated isobutylene polymer thus obtained was mixed with 60 g of a paraffin-based process oil (manufactured by Idemitsu Kosan Co., Ltd., trade name: Diana Process PS-32) as a hydrocarbon plasticizer. 7
After the temperature was raised to 5 ° C, methyldimethoxysilane 1.5
[Eq / vinyl group], platinum (vinylsiloxane) complex 5x
10 ^-5 [eq / vinyl group] was added to perform a hydrosilylation reaction. The reaction was followed by FT-IR, and the olefin absorption at 1640 cm ^-1 disappeared in about 20 hours.

A desired mixture (weight ratio of 10/3) of isobutylene polymer having a reactive silicon group at both ends (the following compound) and PS-32 as a plasticizer was obtained.

[0082]

Embedded image

The yield was calculated from the yield of the polymer thus obtained, and Mn and Mw / Mn were determined by GPC and the terminal structure was determined by 300 MHz ¹ H-NMR analysis. Proton: 6.5 to 7.5 ppm, methyl proton bonded to a silicon atom derived from a polymer end: 0.0 to 0.1 ppm
And methoxy protons: 3.4 to 3.5) were obtained by measuring and comparing the intensity of the resonance signals. ¹ H-NMR
Is a Varian Gemini 300 (300 MHz
for ¹ H) in CDCl ₃ .

The FT-IR is IR-4 manufactured by Shimadzu Corporation.
08, GPC is Waters LC
Module 1, column is Shodex K-804
This was performed using Molecular weights are given as relative molecular weights to polystyrene standards. The analytical value of the polymer is
Mn = 5780, Mw / Mn = 1.28, Fn (silyl) = 1.93. (The number average molecular weight is in terms of polystyrene, the number of terminal silyl functional groups is isobutylene polymer 1
Number per molecule).

Production Example 2 The addition amounts were 262.5 ml of ethylcyclohexane, 787.5 ml of toluene, and 438 ml of isobutylene monomer.
(5.15 mol), p-DCC 4.85 g (21.0
mmol), 0.72 g of 2-methylpyridine (7.7 m
mol), 7.20 g of allyltrimethylsilane (63.
Allyl-terminated isobutylene-based polymer was synthesized in the same manner as in Production Example 1 except that the amount was changed to 0 mmol).

Next, 400 g of the allyl-terminated isobutylene polymer thus obtained was mixed with 200 g of a paraffin-based process oil (manufactured by Idemitsu Kosan Co., Ltd., trade name: Diana Process PS-32) as a hydrocarbon plasticizer. After the temperature was raised to 75 ° C., methyldimethoxysilane 2.4
[Eq / vinyl group], platinum (vinylsiloxane) complex7.
5 × 10 ⁻⁵ [eq / vinyl group] was added to perform a hydrosilylation reaction. The reaction was tracked by FT-IR,
At 0 hours, the olefin absorption at 1640 cm ^-1 disappeared.

A desired mixture (2/1 weight ratio) of isobutylene polymer having reactive silicon groups at both ends (the characteristics are shown below) and PS-32 as a plasticizer was obtained. The analytical value of the polymer was Mn = 17600, M
w / Mn = 1.23 and Fn (silyl) = 1.96.

Examples 1 to 3 and Comparative Example 1 The reactive hydrocarbon group-containing saturated hydrocarbon polymer (PIB) of component (A) obtained in Production Example 1 and a paraffin-based process oil (Idemitsu Kosan Co., Ltd.) (Trade name: Diana Process PS-32) (weight ratio: PIB / PS-32)
= 10/3) and N-phenyl-γ-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name KBM-57) which is a silane coupling agent of the component (B).
3), tetra-n-butyl titanate which is an organic titanate of the component (C) (Wako Pure Chemical Industries, Ltd.),
(D) Dibutyltin bisacetylacetonate (manufactured by Nitto Kasei Co., Ltd., trade name: Neostan U-220) as a silanol condensation catalyst of the component, and n-hexane (Wako Pure Chemical Industries, Ltd.) as a solvent. Mix at the weight ratio shown in 1,
A primer composition was prepared.

On the other hand, a main agent and a curing agent for an isobutylene-based sealing material were prepared by the following method, and an adhesion test was performed using this sealing material. Mixture of reactive hydrocarbon group-containing saturated hydrocarbon polymer (PIB) of component (A) obtained in Production Example 2 and paraffin-based process oil (Diana Process PS-32, trade name, manufactured by Idemitsu Kosan Co., Ltd.) (Weight ratio: PIB / PS-32 = 2/1) 150 parts, 60 parts of hydrogenated α-olefin oligomer (PAO5004, trade name, manufactured by Idemitsu Petrochemical Co., Ltd.), colloidal calcium carbonate (Maruo Calcium Co., Ltd.) ), 50 parts of trade name SEILLETS 200), 50 parts of colloidal calcium carbonate (manufactured by Maruo Calcium Co., Ltd., trade name: MC-5), heavy calcium carbonate (manufactured by Shiroishi Calcium Co., Ltd., trade name: Softon 320
0) 40 parts, epoxy resin (Yuika Shell Epoxy Co., Ltd.)
5 parts, photocurable resin (trade name ARONIX M-309, manufactured by Toagosei Co., Ltd.)
1 part of a hindered phenolic antioxidant (manufactured by Nippon Ciba Geigy Co., Ltd., trade name: Irganox 1010)
1 part of benzotriazole-based ultraviolet absorber (trade name: Tinuvin 327, manufactured by Nippon Ciba Geigy Co., Ltd.), hindered amine light stabilizer (trade name: Sanol LS-, manufactured by Sankyo Co., Ltd.)
770) 1 part and 5 parts of H ₂ O were weighed and mixed with each other, and kneaded three times with a small three paint roll to obtain a composition as a main ingredient.

As curing agents, 3 parts of tin octylate (Neostan U-28, manufactured by Nitto Kasei Co., Ltd.), 0.75 part of laurylamine (Wako Pure Chemical Industries, Ltd.), paraffin-based process oil (Idemitsu) 6.25 parts of Diana Process PS-32 manufactured by Kosan Co., Ltd., heavy calcium carbonate (Softon 3200 manufactured by Shiraishi Calcium Co., Ltd.)
10 parts, 10 parts of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., trade name: Typaque R-820), and 10 parts of carbon black (manufactured by Mitsubishi Chemical Corporation, trade name: carbon black # 30) were measured and mixed. The composition was kneaded with a small homogenizer to obtain a curing agent.

The tensile adhesion test method was evaluated by the following method. Float glass conforming to JIS A-5758 (manufactured by Koensha: Designated by Japan Sealing Material Association, dimensions: 5
× 5 × 0.5cm) or anodized aluminum (manufactured by Koen):
Designated by Japan Sealant Manufacturers Association, dimensions: 5 x 5 x 0.5c
m) was washed with methyl ethyl ketone (Wako Pure Chemical Industries, Ltd.), and the primer shown in Table 1 was applied once. The primer and the curing agent of the above-mentioned isobutylene-based sealing material were weighed in a weight ratio of 100/10, and the mixture was sufficiently kneaded on a primer layer formed by leaving the coating at 23 ° C. for 1 hour or more. Coated in thickness and cured in oven. The curing conditions are all 23 ° C. × 2 days + 50 ° C. × 4 days. After curing, a hand peel test was performed while cutting the adhesive surface with a cutter knife. Observe the peeled substrate surface,
The ratio of the cohesive failure portion was defined as the cohesive failure rate (%). Table 1 summarizes the composition of the primer and the measurement results of the adhesion test.

[0092]

[Table 1]

The primer composition shown in Comparative Example 1 has poor adhesion to float glass and anodized aluminum, and the cohesive failure rate is 0% in each case. On the other hand, the primer compositions of Examples 1 to 3 containing a saturated hydrocarbon polymer having at least one reactive silicon group as the component (A) have relatively good adhesiveness and a cohesive failure rate of 40. % Or more. As described above, the primer composition containing the saturated hydrocarbon-based polymer having at least one reactive silicon group as the component (A) has good adhesion to various base materials, and is particularly suitable for isobutylene-based sealing materials. Shows the effect when applied.

Production Example 3 An allyl-terminated isobutylene polymer was obtained in the same manner as in Production Example 1, and the resulting allyl-terminated isobutylene polymer-1 was obtained.
20 g was heated to 90 ° C., and 1.5 [eq / vinyl group] of methyldimethoxysilane and 5 × 10 ⁻⁵ [eq / vinyl group] of a platinum (vinyl siloxane) complex were added, and a hydrosilylation reaction was performed. The reaction was tracked by FT-IR and 5
Over time, the olefin absorption at 1640 cm ^-1 disappeared. The desired isobutylene polymer having reactive silicon groups at both ends was obtained. Analyze the polymer in the same way,
Mn = 5800, Mw / Mn = 1.35, Fn (silyl) = 1.90. (The number average molecular weight is in terms of polystyrene, the number of terminal silyl functional groups is isobutylene polymer 1
Number per molecule).

Example 4 The saturated hydrocarbon polymer having a reactive silicon group of the component (A) obtained in Production Example 3 and N-phenyl-γ-aminopropyl as the silane coupling agent of the component (B) were used. Trimethoxysilane (brand name KBM-, manufactured by Shin-Etsu Chemical Co., Ltd.)
573), tetra-n-butyl titanate (Wako Pure Chemical Industries, Ltd.) which is an organic titanate of component (C), and dibutyltin bisacetylacetonate which is a silanol condensation catalyst of component (D) (Nitto Kasei Manufactured by
Product name Neostan U-220) and n as solvent
-Hexane (Wako Pure Chemical Industries, Ltd.) was mixed at a weight ratio shown in Table 2 to prepare a primer composition.

Example 5 A primer composition was prepared in the same manner as in Example 4 except that the component (D) was di-n-butyltin dimethoxite (trade name: SCAT-27, manufactured by Sankyoki Gosei Co., Ltd.). Prepared.

Example 6 The component (D) was used as a reaction mixture of di-n-butyltin oxide and dialkyl phthalate (manufactured by Sankyoki Gosei Co., Ltd.).
Product name No. Except for 918), a primer composition was prepared in the same manner as in Example 4.

Adhesion Evaluation Method in Examples 4 to 6 Float glass conforming to JIS A-5758 (manufactured by Koensha, designated by the Japan Sealing Material Manufacturers Association, dimensions: 5 × 5 ×
0.5 cm) and anodized aluminum (manufactured by Koen Co., Ltd., designated by the Japan Sealing Material Manufacturers Association, dimensions: 5 × 5 × 0.5 cm) were each washed with methyl ethyl ketone (Wako Pure Chemical Industries, Ltd.). The primer was applied once. After drying at room temperature for 60 minutes, the mixture was assembled into an H-form conforming to JIS A-1439, and the main agent and the curing agent of the above-mentioned isobutylene-based sealing material were weighed in a weight ratio of main agent / curing agent = 100/10 and kneaded sufficiently. Fill it to make a test specimen, 23 ° C x 3 days +
After curing at 50 ° C. for 4 days, a tensile test was performed. In addition, three types of silicone-based sealing materials having a size of 4 × 3 × 1 cm that have been sufficiently cured and cured (manufactured by Yokohama Rubber Co., Ltd.
Trade name silicone 70; made by Toshiba Silicone, trade name Tosseal 361; made by Toray Dow Corning, trade name SE-7
92) was cut into two pieces each with a cutter knife (dimensions: 4 × 3 × 0.5 cm), and the cut surfaces were washed with toluene (Wako Pure Chemical Industries, Ltd.), and then the primers shown in Table 2 were used. One application was performed. On the primer layer formed by leaving the film at 23 ° C. for 1 hour or more, the main agent and the curing agent of the above-mentioned isobutylene-based sealing material were mixed with the main agent / curing agent = 100/10
The mixture was weighed at a weight ratio of 1 and kneaded well, and the mixture was applied to a thickness of 5 mm and cured in an oven. The curing conditions are all 23 ° C. × 3 days + 50 ° C. × 4 days. After curing, a hand peel test was performed while cutting the adhesive surface with a cutter knife. The surface of the peeled substrate was observed, and the ratio of the cohesive failure portion was defined as the cohesive failure rate (%). Table 2 shows the measurement results of the adhesion test for the float glass and the anodized aluminum and the measurement results of the joint adhesion test for the silicon-based sealing material together with the composition of the primer.
In the table, AF (adhesion failure)
Indicates a state where the adherend and the cured product are separated, and CF (coh
"Ession failure" indicates a state in which the cured product itself is broken.

[0099]

[Table 2]

[0100]

The primer composition of the present invention can remarkably improve the adhesion to various substrates. The effect is particularly useful when applied to an isobutylene-based sealing material.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // B32B27 / 32 B32B27 / 32 A C08L 83:04

Claims (9)

[Claims] 1. A saturated hydrocarbon polymer having (A) a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having at least one silicon-containing group capable of crosslinking by forming a siloxane bond. A primer composition comprising: 2. The primer composition according to claim 1, further comprising a silane coupling agent as the component (B). 3. The primer composition according to claim 1, further comprising an organic titanate as component (C). 4. The primer composition according to claim 1, further comprising a silanol condensation catalyst as the component (D). 5. The saturated hydrocarbon polymer as the component (A),
The number average molecular weight is in the range of 500 to 50,000, and at the terminal of the main chain and / or the terminal of the side chain, a compound represented by the general formula (1) (Wherein, R ¹ and R ² each independently represent a carbon atom of 1
20 alkyl group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms (R ') ₃ SiO-
(R ′ is each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms). X is each independently a hydroxyl group or a hydrolyzable group. Further, a is 0, 1,
B is 0, 1, or 2, and a and b do not become 0 at the same time. Also, m
The primer composition according to claim 1, wherein the primer composition has at least one hydrolyzable silyl group represented by the following formula: 6. The saturated hydrocarbon polymer as component (A),
The primer composition according to claim 1, wherein the total amount of the repeating units derived from isobutylene is 50% by weight or more. 7. The silane coupling agent as the component (B),
3. A silane coupling agent containing an isocyanate group and / or a silane coupling agent containing an amino group.
The primer composition according to any one of the preceding claims. 8. (A) 100 parts by weight of a saturated hydrocarbon polymer having at least one silicon-containing group capable of crosslinking by forming a siloxane bond, having a hydroxyl group or a hydrolyzable group bonded to a silicon atom. The primer composition according to claim 2, further comprising (B) 0.1 to 10000 parts by weight of a silane coupling agent. 9. After coating the primer composition according to claim 1 on a substrate, the primer composition is crosslinked by forming a siloxane bond having a hydroxyl group or a hydrolyzable group bonded to a silicon atom on the coated surface. A method for bonding a sealing material to a substrate, comprising bonding a sealing material containing a saturated hydrocarbon polymer having at least one silicon-containing group as a main component to be obtained.