JP2002173630A - Primer composition and method for bonding the same composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a primer composition effective for favorably bonding a cured product of curable composition crosslinked by hyrosilylation reaction to various substrates and a bonding method. SOLUTION: This primer composition comprises (A) a saturated hydrocarbon- based polymer having at least one alkenyl group in one molecule, (B) a silane coupling agent, (C) a polyvalent alkoxysilane and/or a condensation product thereof and (D) an organoaluminum compound and/or an organotitanium compound or this primer composition comprises the components (B), (C) and (D) and further (E) a vinyl copolymer having a backbone structure substantially comprised of a vinyl copolymer chain and containing a silicon-containing group having a hydroxyl or hydrolyzable group bound to a silicon atom and capable of crosslinking by siloxane bonding terminally of its backbone chain and/or in its side chain. This method for bonding the cured product to a substrate comprises coating a primer composition comprising the component(B) or the components (C) and (D) on a substrate and applying a curable composition comprising a saturated hydrocarbon-based polymer having at least one alkenyl group in the molecule onto the primed substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a primer composition effective for adhering an addition-reaction type saturated hydrocarbon polymer to various base materials and a method for adhering the primer composition. Primer technology to improve the adhesion to the base material and the addition of the addition type curable composition of the saturated hydrocarbon polymer after applying the primer to the base material, and then curing, to improve the adhesion of the addition type cured product Related to technology.

[0002]

2. Description of the Related Art Curable compositions in which a saturated hydrocarbon polymer having at least one alkenyl group in the molecule is crosslinked with a curing agent having a hydrogen atom bonded to two or more silicon atoms in the molecule ( Additive curable compositions) are disclosed in JP-A-2-75644, JP-A-3-181565, and the like. A cured product of the composition (also referred to as an addition-type cured product) has excellent weather resistance, heat resistance, low moisture permeability, and the like, and is expected to be used for a wide range of applications.

[0003] In particular, when an addition-type curable composition of a saturated hydrocarbon polymer is used as a coating and dipping material or a sealing material for various materials, adhesion to various substrates is required. As a technique for imparting adhesiveness to an addition-type curable composition of a saturated hydrocarbon polymer, a technique of blending various adhesion improvers into the addition-type curable composition is disclosed. For example, JP-A-4-185687 discloses a method of adding a silane coupling agent to an addition-type curable composition, and JP-A-08-134165 discloses the addition of a nitrogen-containing epoxy compound and a silane coupling agent. JP-A-08-134165, a method of adding an isocyanate-containing compound and a silane coupling agent to JP-A-08-134165, and JP-A-09-316293 and JP-A-10-204222 disclose a silane coupling agent for an addition-type curable composition. And a method of adding an alkoxysilane condensate and an organoaluminum and / or organotitanium compound. These methods have problems such as curing delay depending on the type of the silane coupling agent.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a saturated hydrocarbon polymer having at least one alkenyl group in a molecule and a curing polymer having two or more silicon-bonded hydrogen atoms in the molecule. It is an object of the present invention to provide a primer composition and a bonding method which are effective for favorably bonding a cured product of a curable composition which is crosslinked by a hydrosilylation reaction and various substrates, containing an agent.

[0005]

Means for Solving the Problems The inventors of the present invention, based on a different idea from the conventional art of formulating an adhesion improving agent, have at least one alkenyl group in a molecule by using a primer composition. It has been found that addition-type curable compositions and addition-type cured products containing a saturated hydrocarbon-based polymer and a curing agent having a hydrogen atom bonded to two or more silicon atoms in the molecule can be bonded to various substrates. .

That is, the present invention provides the following component (A):
(B) a primer composition comprising (C) and (D) as essential components; (A) a saturated hydrocarbon polymer having at least one alkenyl group in one molecule (B) a silane coupling agent (C) The present invention relates to (D) an organoaluminum compound and / or an organotitanium compound.

Further, in the present invention, a primer composition further comprising a component (E) in addition to the components (B), (C) and (D); (E) the main chain is substantially composed of a vinyl copolymer chain. The present invention relates to a vinyl copolymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom at a terminal and / or a side chain of the main chain and containing a silicon-containing group which can be crosslinked by forming a siloxane bond. In the present invention, the vinyl copolymer as the component (E) further has a number average molecular weight of 500 to 50.
000, and at the end of the main chain and / or at the end of the side chain, a compound represented by the general formula (1):

[0008]

Embedded image

(Wherein R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or (R ′) ₃ SiO- (R 'is each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms), and X is a triorganosiloxy group.
Each is independently a hydroxyl group or a hydrolyzable group. Further, a is 0, 1, 2, 3, and b is 0,
It is either 1 or 2, and a and b do not become 0 at the same time. M is 0 or an integer of 1 to 19)
A saturated hydrocarbon having at least one alkenyl group in one molecule, which is the component (A), in addition to the components (B) to (E). It is preferable to further contain a system polymer.

Further, in the present invention, (A) component saturated hydrocarbon polymer of a number average molecular weight of 500 to 5000
It is preferably in the range of 0, and is preferably a polyisobutylene-based polymer containing at least one alkenyl group at the terminal of the main chain and / or the terminal of the side chain.

In the present invention, the silane coupling agent as the component (B) is a silane coupling agent containing an epoxy group, a vinyl group or a (meth) acryloyl group, and one or more silane coupling agents. It preferably comprises

Further, in the present invention, it is preferable to further contain a hydrosilylation catalyst as the component (F).

Further, the present invention relates to a saturated hydrocarbon system having at least one alkenyl group in a molecule after applying a primer composition comprising the component (B) as an essential component on a substrate. The present invention relates to a method for bonding a cured product to a substrate, which comprises bonding a curable composition containing a polymer.

In the present invention, in addition to the primer component (B), the component (C) is a polyvalent alkoxysilane and / or a condensate thereof, and the component (D) is an organoaluminum compound and / or It is preferred to add an organic titanium compound. Furthermore, it is preferable to contain a hydrosilylation catalyst as the component (F), and it is more preferable to contain an organic solvent as the component (G).

In the present invention, after a primer composition comprising the components (C) and (D) as essential components is applied to a substrate, the applied surface has at least one alkenyl group in the molecule. The present invention relates to a method for bonding a cured product to a substrate, which comprises bonding a curable composition containing a saturated hydrocarbon polymer.

In the present invention, the saturated hydrocarbon polymer having at least one alkenyl group in the molecule is a polyisobutylene polymer having an alkenyl group at the terminal of the main chain and / or the terminal of the side chain. And the number average molecular weight is 5
It is preferably from 00 to 50,000.

In the present invention, the silane coupling agent of the component (B) is a silane coupling agent containing an epoxy group, a vinyl group or a (meth) acryloyl group, and one or more silane coupling agents may be used. It preferably comprises a ring agent.

Further, the present invention relates to a cured product obtained by bonding the substrate and the cured product obtained by the above-mentioned bonding method.

[0019]

Next, the primer composition and the addition-type curable composition of the present invention will be described in detail. The component (A) used in the present invention is a saturated hydrocarbon polymer having at least one alkenyl group capable of undergoing a hydrosilylation reaction in the molecule. An alkenyl group capable of performing a hydrosilylation reaction is defined as a carbon atom active for a hydrosilylation reaction.
The group is not particularly limited as long as the group contains a carbon double bond. Examples of the alkenyl group include an aliphatic unsaturated hydrocarbon group such as a vinyl group, an allyl group, a methylvinyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group. And the like. In the present invention, the component (A) desirably has 1 to 10 alkenyl groups in one molecule.

The polymer constituting the skeleton of the saturated hydrocarbon polymer as the component (A) includes (1) ethylene, propylene,
-Polymerizing an olefinic compound having 1 to 6 carbon atoms such as butene and isobutylene as a main monomer,
(2) hydrogenation after homopolymerizing a diene compound such as butadiene or isoprene, or copolymerizing the olefin compound and the diene compound,
However, the isobutylene-based polymer and the hydrogenated polybutadiene-based polymer can be obtained from the viewpoints of easily introducing a functional group into the terminal, controlling the molecular weight, and increasing the number of terminal functional groups. It is desirable to be a coalesced or hydrogenated polyisoprene polymer.

In the above-mentioned isobutylene-based polymer, all of the monomer units may be formed from isobutylene units, and the monomer units having copolymerizability with isobutylene are preferably 50% ( wt%, hereinafter the same) or less, more preferably 30% or less, particularly preferably be incorporated within a range of 20% or less.

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. Specific examples of such a copolymer component include, for example, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, and 4-methyl-
1-pentene, hexene, vinylcyclohexane, methylvinyl ether, ethylvinyl ether, isobutylvinyl ether, styrene, α-methylstyrene, dimethylstyrene, pt-butoxystyrene, p-hexenyloxystyrene, p-allyloxy Styrene, p-hydroxystyrene, β-pinene, indene, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3
Divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldimethoxysilane, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and the like.

In the hydrogenated polybutadiene-based polymer and other saturated hydrocarbon-based polymers, similarly to the case of the isobutylene-based polymer, in addition to the monomer unit as a main component,
Other monomer units may be contained.

Further, the saturated hydrocarbon polymer to be used as in the present invention component (A), the purpose remains butadiene in coverage achieved, the polymerization after the double bonds such as a polyene compound such as isoprene of the present invention A small amount of such monomer units,
Preferably, it may be contained in a range of 10% or less.

The number average molecular weight (GPC method, in terms of polystyrene) of the saturated hydrocarbon polymer, preferably isobutylene polymer, hydrogenated polyisoprene or hydrogenated polybutadiene polymer is 100,000 or less, and more preferably 500 to 1
It is preferably about 00000, particularly 1000 to 4
A liquid material having a fluidity of about 0000 and a fluidity are preferable from the viewpoint of easy handling.

The method for producing the component (A) of the present invention is described in JP-A-3-152164 and JP-A-7-30490.
(9) A method of reacting a polymer having a functional group such as a hydroxyl group with a compound having an unsaturated group and introducing an unsaturated group into the polymer as disclosed in each of the publications. In addition, a method of performing a Friedel-Crafts reaction with alkenyl phenyl ether to introduce an unsaturated group into a polymer having a halogen atom, a method of performing a substitution reaction with allyltrimethylsilane in the presence of a Lewis acid, various phenols and Friedel A method in which a crafts reaction is performed to introduce a hydroxyl group, and then the above-described alkenyl group introduction method is further used in combination. Further, U.S. Pat. No. 4,316,973, JP-A-63-105
No. 005 and Japanese Unexamined Patent Publication (Kokai) No. 4-288309 can introduce a method of introducing an unsaturated group during polymerization of a monomer.

The silane coupling agent (B) used in the present invention is selected from the group consisting of an epoxy group, a methacryl group, an acryl group, an isocyanate group, an isocyanurate group, a vinyl group and a carbamate group in the molecule. A silane coupling agent having at least one functional group and a silicon-bonded alkoxy group is preferred. Regarding the functional groups, among others, from the viewpoint of curability and adhesiveness,
An epoxy group, a vinyl group, a methacryl group, and an acryl group are particularly preferable in the molecule. Specifically, examples of the organosilicon compound having an epoxy functional group and a silicon-bonded alkoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2- (3,4-epoxy). Cyclohexyl) ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane. Also,
Examples of the organosilicon compound having a vinyl group and a silicon-bonded alkoxy group include vinyltrimethoxysilane and vinyltriethoxysilane. The organic As the silicon compound 3-methacryloxypropyl trimethoxysilane having a methacryl group or an acryl group and a silicon-bonded alkoxy group, 3-methacryloxypropyl triethoxysilane, 3-acryloxy propyl trimethoxy silane, 3-acrylic Roxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane,
Examples include methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, and acryloxymethyltriethoxysilane.

The polyalkoxysilane as the component (C) in the present invention is a compound having only a group selected from an alkyl group and an alkoxy group as a substituent on silicon. A hydrolyzate or a partial hydrolyzate thereof further includes dehydration-condensation (silanol condensation). As the polyvalent alkoxysilane as the component (C), specifically, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra (n-propyloxy) silane, tetra (n-butoxy) silane and condensates thereof or Examples include trialkoxysilanes such as methyltriethoxysilane and ethyltriethoxysilane and condensates thereof.

Further, examples of the condensation catalyst which is the component (D) of the present invention include organic aluminum compounds and organic titanium compounds. As the organoaluminum compound, a chelate organic compound which is a useful catalyst for a hydrolysis-condensation reaction of an alkoxysilyl group is preferable. Specific examples include aluminum acetylacetonate. As the organic titanium compound, an organic titanium compound having a Ti—O—C bond, which is a useful catalyst for a hydrolysis-condensation reaction of an alkoxysilyl group, is preferable. Specific examples include tetraalkoxytitanium such as tetraisopropoxytitanium and tetrabutoxytitanium, and general titanate coupling agents such as those having a residue such as oxyacetic acid and ethylene glycol.

The vinyl copolymer having a reactive silicon group of the component (E) of the present invention (hereinafter referred to as a silyl group-containing vinyl polymer) has a main chain substantially consisting of a vinyl polymer chain. Segments other than those comprising vinyl-based monomer units, such as segments comprising a urethane bond or a siloxane bond in the main chain, substantially impart the characteristics of a vinyl polymer to a silyl group-containing vinyl polymer. This means that it may be contained within a range that does not impair, and generally, a segment other than a segment composed of a vinyl monomer unit is contained in a range of about 50 atom% or less of the atoms constituting the main chain. The properties as a vinyl polymer are not substantially impaired. As described above, since the main chain is substantially composed of a vinyl polymer, the primer is excellent in durability and chemical resistance.

The reactive silicon group is represented by the general formula (1):

[0032]

Embedded image

(Wherein R ¹ and R ² each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO- (R 'is each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms), and X is a triorganosiloxy group.
Each is independently a hydroxyl group or a hydrolyzable group. Further, a is 0, 1, 2, 3, and b is 0,
It is either 1 or 2, and a and b do not become 0 at the same time. M is 0 or an integer of 1 to 19)
And the group represented by

As the hydrolyzable group, for example, a hydrogen atom, a halogen 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 generally used. Group.

Of 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 silicon atom forming the reactive silicon group is 1
The number is preferably at least 20, but in the case of silicon atoms linked by a siloxane bond or the like, the number is preferably at most 20. In particular, the general formula (2)

[0038]

Embedded image

(Wherein R ² , X and a are as defined above) are preferred because they are easily available.

Further, a hydrolyzable silyl group may be added to the main chain terminal and / or side chain of the silyl group-containing vinyl polymer.
Having at least one in the molecule means that at least one, preferably two, per molecule is located at the terminal or side chain of the main chain of the polymer.
That is, it has at least two hydrolyzable silyl groups. Since it has at least one hydrolyzable silyl group per molecule, it has a high molecular weight or gels in the presence of moisture, generates chemically stable siloxane bonds, and improves the chemical resistance and the like of the coating film. Further, the hydrolyzable silyl group has a good affinity for the inorganic base material and causes a cross-linking reaction due to the presence of water, so that the coating film has an effect of good adhesion to the inorganic base material.

The number average molecular weight of the silyl group-containing vinyl polymer is preferably about 500 to 50,000, and more preferably about 1,000 to 20,000 from the viewpoint of easy handling.

The glass transition point (Tg) of the polymer is not particularly limited. For example, when the Tg is lowered to 10 ° C. or less, a characteristic that the polymer has low shrinkage is produced. When the temperature is as high as 30 ° C. or more, characteristics such as improvement of chemical resistance, water resistance, and reinforcing property of the base material arise.

[0043] The method for producing the silyl group-containing vinyl polymer, such as there are various ways. For example,
(I) a method of producing by copolymerizing a vinyl monomer and a hydrolyzable silyl group-containing monomer (hereinafter, referred to as a silyl group-containing monomer); (ii) a vinyl monomer and a reactive functional group (hereinafter, referred to as an X group) A monomer having a functional group capable of reacting with a reactive silicon group and an X group [eg, having an isocyanate group and a -Si (OCH ₃ ) group] Compound].

The vinyl monomer is not particularly limited, but specific examples thereof include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t- Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, trifluoroethyl (meth) acrylate, pentafluoropropyl ( Esters of unsaturated carboxylic acids such as di- or half-esters of meth) acrylates, polycarboxylic acids (maleic acid, fumaric acid, itaconic acid, etc.) with linear or branched alcohols having 1 to 20 carbon atoms; styrene, α Methyl styrene, chlorostyrene,
Aromatic hydrocarbon-based vinyl compounds such as styrene sulfonic acid, 4-hydroxystyrene and vinyl toluene; vinyl esters and allyl compounds such as vinyl acetate, vinyl propionate and diallyl phthalate; vinyl compounds containing a nitrile group such as (meth) acrylonitrile; Epoxy group-containing vinyl compounds such as glycidyl (meth) acrylate; amino group-containing vinyl compounds such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, vinylpyridine and aminoethyl vinyl ether; (meth) acrylamide, itaconic acid diamide , Α-ethylacrylamide, methacrylamide,
Amide group-containing vinyl compounds such as crotonamide, maleic acid diamide, fumaric acid diamide, N-vinylpyrrolidone, N-butoxymethyl (meth) acrylamide, N, N-dimethylacrylamide, N-methylacrylamide, acryloylmorpholine; 2-hydroxy Ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, Alonix 5700 (produced by Toa Gosei Chemical Industry Co., Ltd.), Pla
ccel FA-1, Placel FA-4, Pla
hydroxyl-containing vinyl compounds such as ccel FM-1 and Placel FM-4 (manufactured by Daicel Chemical Industries, Ltd.);
(Meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, salts thereof (alkali metal salts, ammonium salts, amine salts, etc.), unsaturated carboxylic acids such as maleic anhydride, acid anhydrides or salts thereof; vinyl methyl Other vinyl compounds such as ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, maleimide, N-vinylimidazole, and vinyl sulfonic acid are exemplified. Of these, alkyl (meth) acrylates having 10 or more carbon atoms, such as lauryl (meth) acrylate and stearyl (meth) acrylate,
It is more preferable to form a coating film that is compatible with a low-polarity curable composition containing a saturated hydrocarbon-based polymer.

For example, when a silyl group-containing vinyl polymer having a low Tg such as 10 ° C. or lower is produced, the vinyl monomer may be butyl acrylate or 2-ethylhexyl (meth) acrylate. It is sufficient to use many vinyl monomers having a low Tg of the homopolymer, and when producing a high Tg having a Tg of 30 ° C. or more, the homopolymer such as methyl methacrylate, ethyl methacrylate, and styrene is used. What is necessary is just to use many vinyl monomers with high Tg.

The silyl group-containing monomer is not particularly limited, but specific examples thereof include, for example,

[0047]

Embedded image

And the like. The method for producing a silyl group-containing vinyl polymer from the silyl group-containing monomer and the vinyl monomer is not particularly limited, and examples thereof include JP-A-54-36395, JP-A-57-36109, and JP-A-58-157810. Can be produced according to the method disclosed in Japanese Patent Application Laid-Open Publication No. H10-210, but using an azo radical initiator such as 2,2'-azobisisobutyronitrile and 2,2'-azobis (2-methylbutyronitrile). Solution polymerization is most preferred because the handling of the initiator is easy and the polymerization reaction product mixture can be used as it is.

In the above production, n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, if necessary,
γ-mercaptopropylmethyldimethoxysilane, γ-
Mercaptopropylmethyldiethoxysilane, (CH ₃
O) ₃ Si—S—S—Si (OCH ₃ ) ₃ , (CH
_The molecular weight can be adjusted using a chain transfer agent such as ₃ O) ₃ Si—S ₈ —S—Si (OCH ₃ ) ₃ .

In particular, when a chain transfer agent having a hydrolyzable silyl group in the molecule, for example, γ-mercaptopropyltrimethoxysilane, a hydrolyzable silyl group can be introduced into the terminal of the silyl group-containing vinyl polymer. .

Examples of the polymerization solvent include hydrocarbons (toluene, xylene, n-hexane, cyclohexane, etc.),
Acetates (eg, ethyl acetate, butyl acetate), alcohols (eg, methanol, ethanol, isopropanol, n-butanol), ethers (eg, ethyl cellosolve, butyl cellosolve, cellosolve acetate), ketones (methyl ethyl ketone, ethyl acetoacetate, acetylacetone) And non-reactive solvents such as diacetone alcohol, methyl isobutyl ketone, and acetone.

[0052] The content of the silyl group-containing vinyl polymer of the primer composition of the present invention is preferably at least 1%, 3%
The above is more preferable, and 5% or more is particularly preferable. The silyl group-containing vinyl polymer may be used alone or in combination of two or more.

The hydrosilylation catalyst which is the component (F) of the present invention is not particularly limited, and any catalyst can be used.

More specifically, solid platinum is supported on a carrier such as chloroplatinic acid, platinum alone, alumina, silica, or carbon black; a platinum-vinylsiloxane complex {for example, Ptn (ViMe ₂ SiOSiMe ₂ V
i) n, Pt [(MeViSiO) ₄ ] m}; platinum-phosphine complex {for example, Pt (PPh ₃ ) ₄ , Pt (P
Bu ₃ ) ₄ }; platinum-phosphite complex {for example, Pt
[P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ (where Me is a methyl group, Bu is a butyl group, Vi is a vinyl group, Ph is a phenyl group, and n and m are integers. Represents),
Pt _{(acac) 2,} also platinum described in U.S. Patent 3,159,601 and in Pat 3159662 of Ashby et al - hydrocarbon complex, and Lamoreaux
No. 3,220,972 to the platinum alcoholate catalyst.

Examples of catalysts other than platinum compounds include
Is RhCl (PPh₃)₃, RhCl ₃, Rh / Al
₂O₃, RuCl₃, IrCl₃, FeCl₃, AlC
l₃, PdCl₂・ 2H₂O, NiCl₂, TiC
l₄And the like. Use these catalysts alone
Even better, it may be used in combination of two or more. In terms of catalytic activity
Chloroplatinic acid, platinum-olefin complex, platinum-vinyl
Loxane complex, Pt (acac)₂Are preferred.

The organic solvent as the component (G) of the present invention is used for adjusting the viscosity of the primer composition to a level suitable for a primer coating operation. The solvent only needs to dissolve the components (A) to (F) of the present invention, and the type thereof is not particularly limited. Specific examples include toluene, xylene, heptane, hexane, hydrocarbon solvents such as petroleum solvents, halogen solvents such as trichloroethylene, ester solvents such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone and the like. Examples include ketone solvents, silicone solvents such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. Of these, toluene, xylene, heptane and hexane are preferred, and hexane is more preferred, in that the components (A) to (F) have good compatibility. These solvents may be used alone or in combination of two or more.

The primer has components (A) to (G), among which there are various combinations. These (A) ~
Among the components (G), the primer composition containing the polymer of the components (A) and (E) is effective as a film-forming component for suppressing the adsorption of the primer to the substrate when the substrate is porous. is there. When the base material is porous, the component (F) may adsorb the hydrosilylation catalyst in the addition-curable composition and cause poor curing, which is effective in this case. The component (G) is effective for adjusting the viscosity of the primer.

The curable composition to which the primer composition of the present invention can be suitably combined contains a saturated hydrocarbon polymer having at least one alkenyl group in the molecule. Further, it is preferable to contain a curing agent.

As the above-mentioned saturated hydrocarbon polymer having at least one alkenyl group in the molecule, the same as the component (A) in the primer composition of the present invention can be used.

[0060] The curing agent, as long as it contains two or more hydrosilyl groups in the molecule, is not limited.
Here, one hydrosilyl group refers to one SiH group.
Therefore, when two hydrogen atoms are bonded to the same Si, it is calculated as two hydrosilyl groups.

As a curing agent, organohydrogenpolysiloxane is one of the preferable ones. Here, the organohydrogenpolysiloxane is
Refers to a polysiloxane having a hydrocarbon group or a hydrogen atom on a Si atom.

[0062]

Embedded image

And the like. Of the above various hydrosilyl group-containing group, if consideration is less likely to impair the compatibility with the saturated hydrocarbon polymer in the hydrosilyl group-containing curing agent is a curing agent of the present invention, in particular those of the following preferable.

[0064]

Embedded image

The number of hydrosilyl groups contained in these curing agents may be at least two in one molecule, but is preferably 2 to 40, more preferably 3 to 30. In the case where the composition of the present invention is cured by a hydrosilylation reaction, if the number of the hydrosilyl groups is less than 2, curing is slow and curing failure often occurs. On the other hand, when the number of the hydrosilyl groups is more than 40, the stability of the curing agent is deteriorated, and a large amount of the hydrosilyl groups remains in the cured product even after curing, which may cause voids and cracks.

In the curable composition used in the present invention, the ratio between the alkenyl group of the saturated hydrocarbon polymer and the hydrosilyl group in the curing agent is usually 1: 0.5 in molar ratio.
１ ： 1: 5, preferably 1: 0.8〜1: 3, more preferably 1: 1１〜1: 2.5.

Further, the curable composition used in the present invention may have, if necessary, other fillers, antioxidants, ultraviolet absorbers, pigments, surfactants, etc., and improve the adhesiveness of the curable composition. For this purpose, an adhesiveness-imparting agent can be appropriately added. Specific examples of the filler include inorganic compounds such as titanium oxide, zinc white, and barium sulfate, and organic fillers such as polypropylene, polyethylene, and polyacrylate. In addition, as an adhesion imparting agent,
Various silane coupling agents that do not inactivate the catalyst, for example, specifically, epoxy-based, olefin-based, methacryl-based, ester-based, and tertiary amine-based silane coupling agents are exemplified. Particularly, in the case of a primer applied to the substrate is not particularly necessary to the adhesive applied to the curable composition, there is no problem even if the adhesive applied to the curable composition.

The bonding method of the present invention is not particularly limited, and examples thereof include the following methods. (1) First, a primer composition is applied to a surface to be adhered to a substrate, and the primer is cured in a temperature range of room temperature to 150 ° C., immediately after application of the primer for 60 minutes. (2) Next, the addition type curable composition of the saturated hydrocarbon-based polymer is applied to the surface to which the primer has been applied, and cured under the curing conditions of the addition type curable composition of the saturated hydrocarbon-based polymer. Glue and cure.

The laminate refers to a laminate in which a base material and an addition-type cured product are adhered to each other using the primer composition. One laminate may be obtained by sealing one substrate with the addition-type cured product, or may be any number of sheets. A laminate in which a substrate is bonded with an addition-type cured product may be used.

As the base material, for example, aluminum, S
US, glass, FRP, polycarbonate, acrylic plate, copper plate and the like can be mentioned.

The primer composition of the present invention can be used as a sealing material, a gasket material, an adhesive, a sealing material, a potting material, various coating materials, a vibration-proof material, etc., low moisture permeability, low moisture absorption, low gas permeability, heat resistance. It can be expected to be used in a wide range of application fields utilizing its properties, weather resistance, electrical insulation, and vibration absorption. Specific applications are not particularly limited, for example, capacitors, lithium batteries, fuel cells, batteries,
Gasket seal materials for chemical plants, engines, fuel tanks, etc., gasket materials for outdoor use such as building seals, rooftop waterproofing, solar cell sealing, pipes, boxes for sealing electric circuits, industrial cans and foods Packing used for lids of cans and bottles, high-performance ink materials such as ink cartridges, coats for protecting the surface of electronic circuits, card materials such as IC cards, and packing materials such as fuel cells that require chemical resistance, such as aluminum. Surface coating materials, sound insulation, anti-vibration sheet materials, roll materials for machinery and electrical equipment,
Examples thereof include a pipe through which a gas such as hydrogen and oxygen passes, and a sealing material for a joint portion.

[0072]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. Examples 1-2 and Comparative Example 1 Examples 1-2 and Comparative Example 1 were blended according to the blending ratio shown in Table 1 to prepare a primer composition. As a method for preparing a primer, an allyl-terminated polyisobutylene having a molecular weight of about 10,000 which is a component (A) synthesized according to JP-A-63-105005 (EP40, manufactured by Kanekachi Chemical Industry Co., Ltd.)
After dissolving OA in hexane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane,
Ethyl silicate 40 (manufactured by Nippon Colcoat Co., Ltd.) as a condensate of 3-methacryloxypropyltrimethoxysilane and polyalkoxysilane as component (C), tetra-n-butyl titanate as component (D) and component (E) As a platinum vinyl siloxane complex catalyst (8.
3 × 10 ⁻⁵ mmol / μl, 3 wt% xylene solution)
Was mixed.

On the other hand, an addition reaction type polyisobutylene-based curable composition was prepared by the following method, and an adhesion test was performed using this composition. Allyl group-terminated polyisobutylene having a molecular weight of about 10,000 (EP, manufactured by Kaneka Corporation)
400A) and 5 g of methyl hydrogen polysiloxane (manufactured by Kanegafuchi Chemical Industry Co., Ltd., CR100) were mixed, 30 g of PAO5010 (manufactured by Idemitsu Petrochemical) was used as a plasticizer, and MARKAO-50 was used as an antioxidant.
1 g of Adeka Argus Co., Ltd., and 26 g of hydrophobically treated wet silica as a filler were thoroughly mixed by hand.
The mixture was kneaded three times with three paint rolls. A platinum vinyl siloxane complex catalyst (8.3 × 10 ⁻⁵ mmol) was added to this formulation.
1 / μl, 3 wt% xylene solution), 55.9 μL, and dimethyl malate (Wako Pure Chemical Industries) 25.1 μL,
By hand mixing and mixing, an addition reaction type polyisobutylene-based curable composition was prepared.

As the tensile adhesion test method, SUS3
After the primer composition was applied once on 04 and aluminum, a film was formed at 110 ° C. for 30 minutes. The curable composition was applied to a thickness of about 3 mm on this primer layer, and cured at 60 ° C. for 40 minutes. 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 it was confirmed whether the adhesion was cohesive failure (CF) or interfacial failure (AF). Table 1 shows the results.

[0075]

[Table 1]

Next, a production example of the vinyl copolymer as the component (E) will be described. (Production Example) 50 g of toluene was charged into a reactor equipped with a stirrer, a thermometer, a nitrogen introduction tube, a dropping funnel, and a cooling tube.
Heated to 110 ° C. Thereafter, a solution in which 30 g of stearyl methacrylate, 70 g of γ-methacryloxypropyltrimethoxysilane, 0.5 g of 2,2′-azobis (2-methylbutyronitrile) and 50 g of toluene were dissolved,
The reactor was continuously added over 3 hours. After completion of the monomer addition, polymerization was carried out for another 2 hours, and the solid content concentration was 50% by weight.
Thus, a solution of a silyl group-containing vinyl polymer having a number average molecular weight (Mn) of 15,000 as determined by GPC (in terms of polystyrene) was obtained.

(Examples 3 to 7, Comparative Example 2)
7, Comparative Example 2 was blended at the blending ratio shown in Table 2 to prepare a primer composition.

As a method for preparing the primer, a vinyl polymer as the component (E) synthesized in the production example was added to the silane coupling agent as the component (B) with 3-glycidoxypropyltrimethoxysilane and vinyltrimethoxysilane as the silane coupling agent. ,
3-methacryloxypropyl trimethoxy silane and (C) (manufactured by Nippon Colcoat Co.) is the component polyvalent alkoxysilane ethyl silicate 40 as condensate and (D) a titanium tetra -n- butyl as the component and the component (F) As a platinum vinyl siloxane complex catalyst (8.
3 × 10 ⁻⁵ mmol / μl, 3 wt% xylene solution)
Were mixed and the solvent was added. When adding the component (A), the component (A) was dissolved in hexane and added.
Adhesion evaluation was performed according to the above method. Table 2 shows the results.

[0079]

[Table 2]

Examples 8 to 17 and Comparative Examples 3 to 5 Examples 8 to 17 and Comparative Examples 3 to 5 were blended according to the blending ratios shown in Tables 3, 4 and 5 to prepare primer compositions. As a method for preparing the primer, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane as the silane coupling agent as the component (B) and the polyalkoxy as the component (C) are used. Ethyl silicate 4 as condensate of silane
0 (manufactured by Nippon Colcoat Co., Ltd.), tetra-n-butyl titanate as the component (D) and a platinum vinylsiloxane complex catalyst (3 wt% xylene solution) as the component (F), and then an appropriate amount of hexane as the component (G) was added. Was. Adhesion evaluation was performed according to the above method. The results are shown in Tables 3, 4 and 5.

[0081]

[Table 3]

[0082]

[Table 4]

[0083]

[Table 5]

As can be seen from the table, it was found that the use of the primer composition of the present invention can ensure the adhesion of various substrates.

[0085]

According to the present invention, as is apparent from the examples,
It is an object of the present invention to provide an adhesion method capable of significantly improving the adhesion of an addition-curable saturated hydrocarbon polymer composition to various substrates.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int. Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 183/00 C09D 183/00 183/05 183/05 (31) Priority claim number Japanese Patent Application No. 2000-294639 ( (P2000-294639) (32) Priority date September 27, 2000 (September 27, 2000) (33) Countries claiming priority Japan (JP)

Claims (29)

[Claims] 1. A primer composition comprising the following components (A), (B), (C) and (D). (A) Saturated hydrocarbon polymer having at least one alkenyl group in one molecule (B) Silane coupling agent (C) Polyvalent alkoxysilane and / or condensate thereof (D) Organoaluminum compound and / or organic Titanium compound 2. The saturated hydrocarbon polymer as the component (A),
The primer composition according to claim 1, which is a polyisobutylene-based polymer having a number average molecular weight in the range of 500 to 50,000 and containing at least one alkenyl group at a terminal of a main chain and / or a terminal of a side chain. 3. The silane coupling agent of the component (B),
Epoxy group, vinyl group and (meth) according to claim 1 or 2 primer composition according comprises at least one functional group selected from the group consisting of acryloyl groups. 4. The primer composition according to claim 1, further comprising (F) a hydrosilylation catalyst. 5. The primer composition according to claim 1, further comprising (G) an organic solvent. 6. A primer composition comprising the following components (B), (C), (D) and (E). (B) a silane coupling agent (C) a polyvalent alkoxysilane and / or a condensate thereof (D) an organoaluminum compound and / or an organotitanium compound (E) a main chain substantially consisting of a vinyl copolymer chain, Vinyl copolymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom at the terminal and / or side chain of the main chain and containing a silicon-containing group which can be crosslinked by forming a siloxane bond. 7. The vinyl copolymer as the component (E) has a number average molecular weight in the range of 500 to 50,000, and has at least one of the general formula (1) at the terminal of the main chain and / or at the terminal of the side chain. Formula 1 (Wherein, R ¹ and R ² each independently represent a carbon atom of 1
To 20 alkyl groups, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (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
Is a 0 or an integer of 1 to 19). 8. The method according to claim 1, wherein (A) at least one
The primer composition according to claim 6, comprising a saturated hydrocarbon polymer having two alkenyl groups. 9. The saturated hydrocarbon polymer as the component (A),
The primer composition according to claim 8, which is a polyisobutylene-based polymer having a number average molecular weight in the range of 500 to 50,000 and containing at least one alkenyl group at a terminal of a main chain and / or a terminal of a side chain. 10. The silane coupling agent as the component (B) has at least one functional group selected from the group consisting of an epoxy group, a vinyl group, and a (meth) acryloyl group. Item 14. The primer composition according to Item. 11. Further, the primer composition according to any one of claims 6-10 containing (F) hydrosilylation catalyst. 12. The primer composition according to claim 6, further comprising (G) an organic solvent. 13. After applying a primer composition containing (B) a silane coupling agent on a substrate, a saturated hydrocarbon polymer having at least one alkenyl group in a molecule is coated on the coated surface. A method for bonding a cured product to a substrate, comprising bonding a curable composition to be contained. 14. The bonding method according to claim 13, wherein (B) the silane coupling agent has at least one functional group selected from the group consisting of an epoxy group, a vinyl group and a (meth) acryloyl group. 15. The saturated hydrocarbon polymer having at least one alkenyl group in the molecule is a polyisobutylene polymer having an alkenyl group at a terminal of a main chain and / or a terminal of a side chain. 15. The bonding method according to 13 or 14. 16. The bonding method according to claim 13, wherein the curable composition further contains a curing agent having a hydrogen atom bonded to two or more silicon atoms in a molecule. . 17. The bonding method according to claim 16, wherein the curing agent is a polyorganohydrogenpolysiloxane containing two or more hydrosilyl groups in a molecule. 18. The primer composition further comprises:
The bonding method according to any one of claims 13 to 17, further comprising (C) a polyvalent alkoxysilane and / or a condensate thereof. 19. The primer composition further comprises:
The bonding method according to any one of claims 13 to 18, further comprising (D) an organic aluminum compound and / or an organic titanium compound. 20. The primer composition according to claim 13, further comprising (F) a hydrosilylation catalyst.
The bonding method according to any one of the above items. 21. The bonding method according to claim 13, wherein the primer composition further contains (G) an organic solvent. 22. A laminate obtained by the bonding method according to any one of claims 13 to 20. 23. (C) a polyvalent alkoxysilane and / or a condensate thereof and (D) an organoaluminum compound and / or
Alternatively, after applying a primer composition containing an organotitanium compound onto a substrate, the applied surface may have at least 1
A method for bonding a cured product to a substrate, comprising bonding a curable composition containing a saturated hydrocarbon polymer having two alkenyl groups. 24. The saturated hydrocarbon polymer having at least one alkenyl group in the molecule is a polyisobutylene polymer having an alkenyl group at a terminal of a main chain and / or a terminal of a side chain. 23. The bonding method according to 23. 25. The bonding method according to claim 23, wherein the curable composition further contains a curing agent having a hydrogen atom bonded to two or more silicon atoms in a molecule. 26. The bonding method according to claim 25, wherein the curing agent is a polyorganohydrogenpolysiloxane containing two or more hydrosilyl groups in a molecule. 27. The primer composition according to claim 23, further comprising (F) a hydrosilylation catalyst.
The bonding method according to any one of the above items. 28. The bonding method according to claim 23, wherein the primer composition further contains (G) an organic solvent. 29. A laminate obtained by the bonding method according to claim 22.