JP3330931B2 - Adhesive composition - Google Patents

Description

The present invention relates to an adhesive composition, and more particularly, to an adhesive composition,
(A) a specific compound having any one of an ether bond, an ester bond, a hydrocarbon bond and a carbonate bond having at least one alkenyl group in the molecule, and (B) having at least two hydrosilyl groups in the molecule. The present invention relates to a compound, (C) a hydrosilylation catalyst, and an adhesive composition containing these (A) to (C) and (D) a silane coupling agent as essential components.

[Conventional technology and issues]

An adhesive is used to bond two objects in various fields such as the automobile, the electronics industry, or medical and construction. In recent years, a curable composition used as a molding material also has a cured body adhered to plastic. As such a curable composition, an adhesive composition containing an organic polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and having a silicon-containing group capable of crosslinking by forming a siloxane bond, Are known.
However, this composition has a problem that moisture is required at the time of curing, and it takes a long time to cure. In order to solve this problem, a polyorganosiloxane having an average of two or more vinyl groups in a molecule is crosslinked with a polyorganohydrogensiloxane having two or more hydrogen atoms bonded to silicon atoms in a molecule. Are developed and used as an adhesive composition by utilizing their excellent weather resistance, water resistance and heat resistance. However, this system is expensive,
Its use is limited due to poor adhesion and easy mold generation.

[Means for solving the problem]

The present invention solves these problems as a result of intensive studies in view of such circumstances, and provides an adhesive composition that is quickly curable and has high adhesiveness.

That is, the present invention provides an adhesive composition containing the following components (A) to (C); (A) in a molecule selected from the following formulas (II), (III), (IV) and (V) A compound having at least one alkenyl group (excluding an organopolysiloxane); (R ¹ is hydrogen or a methyl group, R ² is a divalent hydrocarbon group having 1 to 20 carbon atoms and may contain one or more ether bonds. R ³ is an aliphatic or aromatic organic group. , A is a positive integer.) A compound having an ether bond represented by the formula (III): (R ¹ is a hydrogen or methyl group, R ² is a divalent hydrocarbon group having 1 to 20 carbon atoms and may contain one or more ether bonds. R ⁴ is an aliphatic or aromatic organic group. , A is a positive integer.) A compound having an ester bond represented by the formula (IV): (R ¹ is hydrogen or a methyl group, R ⁵ is an aliphatic or aromatic organic group, and a is a positive integer.) A compound represented by the formula (V) (R ¹ is hydrogen or a methyl group, R ² is a divalent hydrocarbon group having 1 to 20 carbon atoms and may contain one or more ether bonds. R ⁶ is an aliphatic or aromatic organic group. , A is a positive integer.), (B) a compound having at least two hydrosilyl groups in the molecule, and (C) a hydrosilylation catalyst.

As the compound having at least one alkenyl group in the molecule, which is the component (A) of the present invention, various compounds ranging from low molecular weight compounds to organic polymers can be used. The alkenyl group is not particularly limited, but has the formula (I) (R ¹ is hydrogen or a methyl group).

When the component (A) is specifically described, first, the formula (II) (R ¹ is hydrogen or a methyl group, R ² is a divalent hydrocarbon group having 1 to 20 carbon atoms and may contain one or more ether bonds. R ³ is an aliphatic or aromatic organic group. , A is a positive integer.).

In the formula (II), R ² represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and R ² may contain one or more ether bonds. _{Specifically, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2 -, _{-CH 2 CH 2 OCH 2 CH 2} -, - CH 2 CH 2 OCH 2 CH 2 CH 2 - and the like. —CH ₂ — is preferred from the viewpoint of ease of synthesis.

In the formula (II), R ³ is an aromatic or aliphatic organic group. Specifically, CH ₃ −, CH ₃ CH ₂ −, CH ₃ CH ₂ CH ₂ −, (N is an integer of 2 to 10). Of these, the following are preferred.

R ³ may be an organic polymer, and various types can be used.

First, as the polyether polymer, for example, polyoxyethylene, polyoxypropylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, or the like is suitably used. Other polymers having a main chain skeleton include polyester polymers, ethylene-propylene copolymers, and polyisobutylenes obtained by condensation of a dibasic acid such as adipic acid with glycol or ring-opening polymerization of lactones. , Copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene and butadiene, acrylonitrile, copolymers of styrene, etc., polybutadiene, butadiene and styrene, copolymers of acrylonitrile and the like, polyisoprene, polybutadiene, Polyolefin polymers obtained by hydrogenating copolymers of isoprene or butadiene with acrylonitrile, styrene, etc., polyacrylates and ethyl acrylates obtained by radical polymerization of monomers such as ethyl acrylate and butyl acrylate Acrylic acid esters such as butyl acrylate,
Acrylic ester copolymers with vinyl acetate, acrylonitrile, methyl methacrylate, styrene, etc., graft polymers obtained by polymerizing vinyl monomers in the organic polymer, polysulfide polymers, ring-opening polymerization of ε-caprolactam 6, Nylon 66 by condensation polymerization of hexamethylenediamine and adipic acid, Nylon 610 by condensation polymerization of hexamethylenediamine and sebacic acid, Nylon 11, and ε-aminolaurolactam by condensation polymerization of ε-aminoundecanoic acid Nylon 12 by polymerization, polyamide polymers such as copolymerized nylon having two or more of the above-mentioned nylons, such as polycarbonate polymers produced by condensation polymerization of bisphenol A and carbonyl chloride, and diallyl phthalate-based polymers. Coalescence and the like are exemplified.

Among these, polyester polymers having an average molecular weight of 500 to 50,000 are preferred, and polycaprolactone is particularly preferred, in that a very high shear adhesive strength can be obtained.

Next, the general formula (III) (R ¹ is hydrogen or a methyl group, R ² is a divalent hydrocarbon group having 1 to 20 carbon atoms and may contain one or more ether bonds. R ⁴ is an aliphatic or aromatic organic group. , A is a positive integer.). In formula (III), R ² is the same as R ² in formula (II). R ⁴ is an aromatic or aliphatic monovalent to tetravalent organic group. Specifically, CH ₃ −, CH ₃ CH ₂ −, CH ₃ CH ₂ CH ₂ −, −CH ₂ CH ₂ −, − (CH ₂ ) ₃ −, − (CH ₂ ) ₄ −, − ( CH ₂ ) ₅ −, −
_{(CH 2) 6 -, -} (CH 2) 7 -, - (CH 2) 8 -, And the like. Of these, the following are preferred.

-(CH ₂ ) ₂ -,-(CH ₂ ) ₃ -,-(CH ₂ ) _6- , R ⁴ may be an organic polymer, and all the organic polymers exemplified by the ether compound of the formula (II) can be suitably used. Among them, polyester-based polymers are preferable, and polycaprolactone is particularly preferable, in that a very good shear adhesive strength can be obtained.

Next, the general formula (IV) (R ¹ is hydrogen or a methyl group, R ⁵ is an aliphatic or aromatic organic group, and a is a positive integer).

In the formula (IV), R ⁵ represents an aliphatic or aromatic organic group. And the like.

Of these,-(CH ₂ ) _n- (n = 1 to 10), Is preferred. Further, — (CH ₂ ) _n — (n = 1 to 10) is particularly preferred.

R ⁵ may be an organic polymer, and all the organic polymers exemplified in the description of the formula (II) can be suitably used.
Among them, polyester polymers are preferable, and polycaprolactone is particularly preferable.

Specific examples of the component (A) further include a compound represented by the general formula (V): (R ¹ is a hydrogen or methyl group, R ² is a divalent hydrocarbon group having 1 to 20 carbon atoms and may contain one or more ether bonds. R ⁶ is an aliphatic or aromatic organic group. , A is a positive integer) having a carbonate bond.

Wherein R ² is the same as R ² in (II). Further, as R ⁶ , CH ₃ −, CH ₃ CH ₂ −, CH ₃ CH ₂ CH ₂ −, − (CH ₂ CH ₂ O) _n CH ₂ CH ₂ − (n is an integer of 1 to 5) − (CH ₂ CH ₂ CH ₂ O) _n CH ₂ CH ₂ CH ₂ − (n is an integer of 1 to 5) − (CH ₂ CH ₂ CH ₂ CH ₂ O) _n CH ₂ CH ₂ CH ₂ CH ₂ − ( n is an integer of 1 to 5). Of these, the following are particularly preferred.

−CH ₂ CH ₂ OCH ₂ CH ₂ −, −CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ −, R ⁶ may be an organic polymer, and all the organic polymers exemplified in the description of the formula (II) can be suitably used.
Of these, polyester polymers are preferred, and polycaprolactone is particularly preferred.

When an organic polymer is used as the component (A), various methods for introducing an alkenyl group into the polymer can be used, but a method introduced after polymerization and a method introduced during polymerization can be used. Methods can be roughly divided.

As a method of introducing an alkenyl group after polymerization, for example, an organic polymer having a functional group such as a terminal group, a main chain or a side chain, such as a hydroxyl group or an alkoxide group, an active group having reactivity with the above functional group, and By reacting an organic compound having an alkenyl group, the alkenyl group can be introduced into the terminal, main chain or side chain. Examples of the organic compound having an active group and the alkenyl group reactive toward the functional groups are acrylic acid, methacrylic acid, vinyl acetate, acrylic acid chloride, unsaturated C ₃ -C _20, such as a bromide acrylate Fatty acids, acid halides, acid anhydrides, etc., C ₃ -C ₂₀ unsaturated fatty acid substituted carbonates such as allyl chloroformate, allyl bromoformate, allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloro) Methyl) benzene, allyl (bromomethyl) benzene, allyl (chloromethyl)
Ether, allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy) benzene, allyloxy (chloromethyl) benzene and the like.

Examples of a method for introducing an alkenyl group during polymerization include, for example, when producing by a radical polymerization method, a vinyl monomer having a low radical reactivity alkenyl group in a molecule such as allyl methacrylate or allyl acrylate, or a radical such as allyl mercaptan. By using a chain transfer agent, an alkenyl group can be introduced into the main chain or terminal of the polymer.

The alkenyl group-containing organic polymer may be linear or branched, and any one having a molecular weight of 500 to 50,000 can be suitably used, and one having a molecular weight of 1,000 to 20,000 is particularly preferable. The alkenyl group may be at the molecular terminal or in the molecule, but when a rubber-like cured product is prepared using the composition of the present invention, the effective network chain length is longer at the molecular terminal. It is preferred.

The organic compound having at least two hydrosilyl groups in the molecule, which is the component (B) of the present invention, is not particularly limited, but specific examples including a hydrosilyl group include -Si (H) _n (CH ₃ ) _3-n , -Si (H) _n (C ₂ H ₅ ) _3-n , -Si (H) _n (C ₆ H ₅ ) _3-n (n = 1 to 3), -SiH ₂ A hydrosilyl group having one silicon atom such as (C ₆ H ₁₃ ), —Si (CH ₃ ) ₂ Si (CH ₃ ) ₂ H, —Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ H , −Si (CH ₃ ) ₂ SiCH ₃ H ₂ , _{-Si (CH 3) 2 NHSi (} CH 3) 2 H, -Si (CH 3) 2 N [Si (CH 3) 2 H] 2, A group containing two silicon atoms, such as (Wherein R is H, OSi (CH ₃ ) _3, and C 1-10)
And each R may be the same or different. m and n are positive integers and 2 ≦ m +
n ≦ 50) (R, m, n are the same as above) (Where R is the same as above, m is a positive integer, n, p, and q are 0 or a positive integer, and 1 ≦ m + n + p + q ≦ 50) (Wherein, R is the same as above, m is a positive number, n is 0 or a positive integer, and 2 <m + n <50) Various chain, branched, and cyclic polyvalent hydrogens represented by, for example, Examples include groups derived from polysiloxane.

Among the above various hydrosilyl groups, the hydrosilyl group-containing organic compound of the present invention has a low possibility of impairing the compatibility with the organic polymer, and the molecular weight of the group constituting the hydrosilyl group is 500 or less. Desirably,
In consideration of the reactivity of the hydrosilyl group, the following compounds are preferred.

(Where p is a positive integer, q is 0 or a positive integer, and 2 ≦ p + q ≦ 4) When two or more hydrosilyl groups are present in the same molecule, they may be the same or different. The number of total hydrosilyl groups contained in the component (B) should be at least two in one molecule, but is preferably 2 to 15, and particularly preferably 3 to 12. When the hydrosilyl group-containing compound of the present invention is mixed with an alkenyl group-containing compound (component (A)) in the presence of a hydrosilylation catalyst and cured by a hydrosilylation reaction, the number of hydrosilyl groups is preferably 2 or less. If the amount is small, curing failure often occurs. When the number of the hydrosilyl groups is more than 15, the stability of the component (B) deteriorates, and a large amount of the hydrosilyl groups remains in the cured product even after curing, which causes voids and cracks.

The hydrosilyl group-containing compound as the component (B) is not particularly limited, but various compounds ranging from low molecular weight compounds to polymers can be used. Specifically,
Equation (VI) (In the formula, X is a group having at least one hydrosilyl group, and R ¹ , R ² , and R ³ are the same as R ¹ , R ² , and R ³ in the formula (II). A compound having an ether bond represented by the formula (VII): (In the formula, X is a group having at least one hydrosilyl group, and R ¹ , R ² , and R ⁴ are the same as R ¹ , R ² , and R ⁴ in the formula (III). A compound having an ester bond represented by the formula (VIII): (Wherein, X is the above group having one or more hydrosilyl group, R ^1, R ⁵ has the formula (in IV), it can be used respectively R ^1, R ⁵ the same thing.) Expressed in And a compound of the formula (IX) (In the formula, X is a group having at least one hydrosilyl group, and R ¹ , R ² , and R ⁶ are the same as R ¹ , R ² , and R ⁶ in the formula (V). And a compound having a carbonate bond represented by the following formula:

When an organic polymer is used as the component (B), the polymer may be linear or branched, and has a molecular weight of 500 to 50,000.
Can be suitably used, but those of 500 to 20,000 are particularly preferred. The hydrosilyl group of the component (B) may be at the molecular terminal or in the molecule, but when a rubber-like cured product is prepared using the composition of the present invention, it is more effective at the molecular terminal. This is preferable because the length of the network chain becomes longer.

The method for producing the component (B) is not particularly limited, and any method may be used. For example, (i) Si—Cl
How an organic compound having a group to process a reducing agent such as LiAlH _4, NaBH ₄ is reduced of Si-Cl group in Yo compound Si-H group, having a functional group X in the (ii) molecules (Iii) a method of reacting an organic compound with a compound having both a functional group Y and a hydrosilyl group that react with the functional group in the molecule.
A method of selectively hydrosilylating a polyhydrosilane compound having at least two hydrosilyl groups with respect to an organic compound having an alkenyl group so that the hydrosilyl group remains in the molecule of the compound even after the reaction can be considered. Among these, the method (iii) is particularly preferred.

As the combination of the component (A) and the component (B), any combination can be used, but the component (A) and the component (B)
It is preferable that one or both of the components is an organic polymer, and among them, a polyester polymer is preferable. When both the component (A) and the component (B) are low molecular weight compounds, the viscosity of the composition becomes too low, which is not preferable as an adhesive composition.

Examples of the hydrosilylation catalyst which is the component (C) of the present invention include: platinum alone, alumina, silica, carbon black or the like on which solid platinum is supported, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone , Platinum-olefin complex {for example, Pt (CH ₂ CHCH ₂ ) _{2
(PPh 3) 2 Pt (CH} 2 = CH 2) 2 Cl 2}; platinum - vinylsiloxane complex {for _{example, Pt n (ViMe 2 SiOSiMe 2} Vi) m, Pt
[(MeViSiO) ₄ ] _m {; platinum-phosphine complex {eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ }; platinum-phosphite complex {eg, Pt [P (OPh ₃ ) ₄ , Pt [ P (OB
u) ₃ ] ₄ ｝ (where Me is a methyl group, Bu is a butyl group, Vi
Represents a vinyl group, Ph represents a phenyl group, and n and m represent integers), dicarbonyldichloroplatinum, and platinum-hydrocarbons described in Ashby U.S. Pat. Nos. 3,159,601 and 3,151,662. Also included are the complexes, as well as the platinum alcoholate catalysts described in Lamoreaux, US Pat. No. 3,209,972. Further, the platinum chloride-olefin complex described in Modic U.S. Pat. No. 3,516,946 is also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PP
_{h 3) 3, RhCl 3,} RhlAl 2 O 3, RuCl 3, IrCl 3, FeCl 3, AlCl 3, PdCl 2
_{· 2H 2 O, NiCl 2,} TiCl 4 , and the like. These catalysts may be used alone or in combination of two or more.
From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complex,
Platinum-vinylsiloxane complexes are preferred.

The amount of the catalyst is not particularly limited, but is preferably in the range of 10 ^-1 to 10 ^-8 mol per ¹ mol of the alkenyl group in the component (A). Preferably, it is used in the range of 10 ^-3 to 10 ^-6 mol. If the amount is less than 10 ^-8 mol, curing does not proceed sufficiently. Further, the hydrosilylation catalyst is generally expensive and humic, and a large amount of hydrogen gas may be generated to cause a cured product to foam. Therefore, it is better not to use 10 ^-1 mol or more.

In the present invention, since the adhesive composition is cured by an addition reaction of an Si-H group to an alkenyl group using a noble metal catalyst, the curing speed is very high.

When the hydrosilyl group-containing compound as the component (B) is produced by the above-mentioned selective hydrosilylation, the stability is generally not good because the hydrosilylation catalyst is contained in the component (B) even after the reaction. If left for a long time or if moisture is mixed in, conversion of Si—H groups to SiOH groups occurs, and phenomena such as an increase in viscosity and gelation are observed. Therefore, it is preferable to include a storage stability improver in the component (B). As such a compound, a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, an organic peroxide, and the like can be suitably used. The amount of the storage stability improver can be almost arbitrarily selected as long as it is uniformly dispersed in the components (A) and (B). It is preferably used in the range of ^-6 to 10 ^-1 mol. This is because if it is 10 ^-6 mol or less, the storage stability of the component (B) is not sufficiently improved, and if it is 10 ^-1 mol or more, curing is inhibited. The storage stability improvers may be used alone or in combination of two or more.

In the present invention, a silane coupling agent such as an acrylic (methacryl) functional silane coupling agent, an epoxy functional silane coupling agent, an amino (imino) functional silane coupling agent, etc. Is blended as a component (D) in the composition.

Specific examples of the acryl (methacryl) functional silane coupling agent include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropylethoxysilane. Methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, and acryloxymethyltriethoxysilane.

Specific examples of epoxy-functional silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3
Glycidoxypropyltriethoxysilane, 2- (3,
Examples thereof include 4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane.

Specific examples of amino (imino) functional silane coupling agents include H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , _{H 2 NCH 2 CH 2 NHCH 2} CH 2 CH 2 Si (CH 3) (OCH 3) 2, (C 2 H 5 O) 3 SiCH 2 CH 2 CH 2 NHCH 2 CH 2 NHCH 2 CH 2 CH 2 Si (OC ₂ H _{5) 3,} amino group etc. and (or) an imino group-containing alkoxysilane, the amino group and (or) and imino group-containing alkoxysilane, Reaction product with an epoxysilane compound such as the above, the above-mentioned alkoxysilane containing an amino group and / or an imino group, and CH ₂ ＣC (CH ₃ ) COOCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CH ₂ ＣC Reaction products with methacryloxysilane compounds such as (CH ₃ ) COOCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₂ OCH ₃ ) ₃ .

The amount of the silane coupling agent used is (A) component and (B)
Is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of

The composition of the present invention may further include a plasticizer, a filler, an antioxidant, an ultraviolet absorber, a metal deactivator, an ozone deterioration inhibitor, a light stabilizer, a lubricant, a pigment, a foaming agent, if necessary. Various additives can be appropriately added to form an adhesive according to the application.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Synthesis Example 1 According to the method disclosed in JP-A-53-134095, polyoxypropylene having an allyl-type olefin group at a terminal was synthesized.

Polyoxypropylene glycol having an average molecular weight of 3000 and powdered caustic soda were stirred at 60 ° C., and bromochloromethane was added to carry out a reaction to increase the molecular weight. next,
Allyl chloride was added, and the terminal was allyl etherified at 110 ° C. This was treated with aluminum silicate to synthesize a purified terminal allyl etherified polyoxypropylene.

The average molecular weight of this polyether was 7,960, and 92% of the terminals were olefin groups based on the iodine value. The viscosity according to the E-type viscosity system was 130 poise (40 ° C.).

Synthesis Example 2 A 14-neck flask equipped with a stirring rod, a dropping funnel, a thermometer, a three-way cock, and a condenser was prepared. Next, under a nitrogen atmosphere, the cyclic polysiloxane 41.7 g (0.173 mol) (LS 8600, manufactured by Shin-Etsu Chemical Co., Ltd.) was charged into the flask. The terminal 92 of the molecule synthesized in Synthesis Example 1
Percent (moles 0.069mol allyl groups) polypropylene oxide 300g an allyl group, an ethanol / 1,2-toluene 230 m, and chloroplatinic acid catalyst solvent chloride _{(H 2 PtCl 6 · 6H 2} O1.0g
83μ dissolved in dimethoxyethane (1/9 V / V) 9G
Was charged into the dropping funnel. Heat the flask to 70 ° C. and allow the toluene solution to
Over 5 hours. Thereafter, the reaction temperature is raised to 80 ° C.
And stirred for about 6 hours, the remaining allyl groups in the reaction solution were quantified by IR spectroscopy.
It was confirmed that the carbon-carbon double bond at 45 cm ^-1 had disappeared. After adding dimethylacetylene carboxylate (118 µ, 0.83 mmol) to the reaction mixture, degassing was performed at 80 ° C for 3 hours under reduced pressure to remove toluene and unreacted excess cyclic polysiloxane in the reaction system. About 315 g of polypropylene oxide having
Obtained as a viscous liquid. The viscosity by E-type viscometer is 31
It was 0 poise (40 ° C). The hydrosilyl group in the polypropylene oxide was confirmed as a strong absorption at 2150 cm ^{-1 in} the IR spectrum. The NMR spectrum at 300 MHz was analyzed, and the combined peak intensity of Si-CH ₃ and Si-CH ₂ -and Si
By comparing the peak intensities of -H, it was found that an average of 1.31 hydrosilyl groups per molecule of the cyclic polysiloxane had reacted. That is, the polymer was increased in one part molecular weight by the cyclic hydrogen polysiloxane,
It is a polypropylene oxide having a molecular terminal represented by the following formula.

Synthesis Example 3 300 g (0.1 mol) of terminal hydroxyl group polycaprolactone (number average molecular weight 3000), 24.0 g of pyridine, 300 m of THF
Was charged into a round bottom flask equipped with a stirring rod, a thermometer, a dropping funnel, a nitrogen blowing tube, and a cooling tube, and at room temperature, 32 g of allyl chloroformate was gradually dropped from the dropping funnel at room temperature.
The mixture was heated to 0 ° C. and stirred for 3 hours. After removing the generated salt by filtration, 150 m of toluene was added, and the mixture was washed with 200 m of hydrochloric acid aqueous solution, neutralized and concentrated to obtain an allyl-terminated polycaprolactone. VPO measurement of the obtained oligomer showed that the number average molecular weight was 3,200. The introduction of the allyl group was confirmed from the spectrum of the olefin portion of the NMR at 300 MHz. Further, from the determination of the olefin by iodine titration, it was confirmed that an average of 2.0 allyl-type unsaturated groups were introduced in one molecule.

Synthesis Example 4 A 300 m four-necked flask equipped with a stirring rod, a dropping funnel, a thermometer, a three-way cock, and a condenser was prepared. Next, under a nitrogen atmosphere, the cyclic polysiloxane 34.55 g (0.1435 mol) (LS 8600, manufactured by Shin-Etsu Chemical Co., Ltd.) was charged in the flask. 100 g of polycaprolactone having an average of 2.0 allyl groups in one molecule synthesized in Synthesis Example 3
(Mol number of olefin: 0.0575 mol), toluene 100 m,
And it was charged chloroplatinic acid catalyst solvent toluene solution consisting of _{(H 2 PtCl 6 · 6H 2} O1g ethanol 1 m, 1,2-dimethoxyethane 9m solution dissolved in) 60 microns into a dropping funnel. The flask was heated to 70 ° C. and the toluene solution was
It was dropped over time. After completion of the dropwise addition, when the mixture was stirred at 80 ° C. for about 5 hours, remaining allyl groups in the reaction solution were quantified by IR spectroscopy. It was confirmed that the carbon-carbon double bond at 1645 cm ⁻¹ had disappeared. Was done. Next, in order to remove the catalyst remaining in the reaction system, 10 g of silica gel (Wako Pure Chemical Industries, Ltd., Wakogel C-200) was added at room temperature, and the mixture was stirred for 2 hours and filtered using a flash column. did. The filtrate was evaporated to remove toluene and excess cyclic polysiloxane, and further devolatilized under reduced pressure at 80 ° C. for 3 hours to obtain a colorless transparent viscous liquid. The hydrosilyl group in the polycaprolactone was 2150 cm in the IR spectrum.
It was confirmed as a strong absorption of ^-1 . The 300MHz of NMR Supukutoru with Si-H peak and Si-CH ₃ and Si-CH ₂ - by comparing the intensities of the peaks of the combined and, cyclic polysiloxane 1 Average 1.05 hydrosilyl groups per molecule reaction I knew it was done. That is, the polymer partially increased in molecular weight by the cyclic hydrogen polysiloxane,
It is a polycaprolactone having a molecular terminal represented by the following formula.

Synthesis Example 5 50 g of toluene was added to 300 g of hydrogenated polyisoprene having a hydrosilyl group at both terminals (Epol, trade name, manufactured by Idemitsu Petrochemical Co., Ltd.), and the mixture was dehydrated by azeotropic degassing. t-BuOK4
A solution obtained by dissolving 8 g in 200 m of THF was injected. After reacting at 50 ° C. for 1 hour, 47 m of allyl chloride was added dropwise over about 30 minutes. After completion of the dropwise addition, 30 g of aluminum silicate was added to the reaction solution to adsorb the generated salt, and the mixture was stirred at room temperature for 30 minutes. Filtration produced about 250 g of allyl-terminated hydrogenated polyisoprene as a viscous liquid. 300 MHz ¹ H NMR analysis confirmed that 92% of the terminal had an allyl group introduced. The number of moles of olefin determined from the iodine value is
It was 0.1072 mol / 100 g. The viscosity measured by E-type viscometer is
It was 302 poise (32 ° C.).

* Typical physical properties of Epol (from technical samples) Hydroxyl content (meq / g) 0.90 Viscosity (poise / 30 ℃) 700 Average molecular weight [VPO measurement] 2500 Synthesis Example 6 Stirrer bar, dropping funnel, thermometer 3, A 300 m four-necked flask equipped with a side cock and a condenser was prepared. Next, under a nitrogen atmosphere, the cyclic polysiloxane 31.5 g (0.131 mol) (LS8600, manufactured by Shin-Etsu Chemical Co., Ltd.) was charged into the flask. Of the molecular end synthesized in Synthesis Example 5
Hydrogenated polyisoprene 50 g 92% is allyl group (number of moles of olefin 0.0536mol), toluene 50m, and chloroplatinic acid catalyst solvent chloride _{(H 2 PtCl 6 · 6H 2} O1g ethanol 1 m, 1, 2
A solution of 60 μm of toluene dissolved in 9 m of dimethoxyethane was charged into the dropping funnel. The flask was heated to 70 ° C. and the toluene solution was added dropwise over about 2 hours. After completion of the dropwise addition, when the mixture was stirred at 80 ° C. for about 5 hours, remaining allyl groups in the reaction solution were quantified by IR spectroscopy. It was confirmed that the carbon-carbon double bond at 1645 cm ⁻¹ had disappeared. Was done. Next, silica gel (Wako Pure Chemical Industries, Ltd.) was used to remove the catalyst remaining in the reaction system.
(Wakogel C-200) at room temperature, stirred for 2 hours and filtered using a flash column. The filtrate was evaporated to remove toluene and excess cyclic polysiloxane, and further degassed under reduced pressure at 80 ° C. for 3 hours to obtain a colorless transparent viscous liquid. The viscosity measured by an E-type viscometer is 51.
It was 4 poise (23 ° C.). The hydrosilyl group in the hydrogenated polyisoprene was confirmed as a strong absorption at 2150 cm ^{-1 in} the IR spectrum. The 300-MHz NMR spectrum shows Si-H
By comparing the peak intensities of the peaks obtained by combining Si—CH ₃ and Si—CH ₂ — with each other, it was found that an average of 1.2 hydrosilyl groups per molecule of the cyclic polysiloxane had reacted. That is, the polymer is a hydrogenated polyisoprene having a molecular terminal represented by the following formula, the molecular weight of which is partially increased by the cyclic hydrogen polysiloxane.

Synthesis Example 7 A four-necked flask equipped with a stirring rod, a dropping funnel, a thermometer, a three-way cock, and a cooling tube was prepared. Next, 20 m of toluene was charged under a nitrogen atmosphere. 2.56 g of n-butyl acrylate, 2.52 g of allyl methacrylate, 0.81 g of n-dodecyl mercaptan, azobisisobutyronitrile
A toluene solution of a monomer consisting of 1.0 g and 100 m of toluene was dropped from the dropping funnel over about 1 hour under reflux of toluene. After the completion of the dropwise addition, the reaction was further continued for 2 hours. After treating the toluene solution with aluminum silicate, a substantially transparent solution was obtained by suction filtration using a filter aid (diatomaceous earth). This solution was evaporated, and further dried under reduced pressure at 80 ° C. for 3 hours to obtain about 26 g of a pale yellow viscous liquid oligomer. The number of moles of allyl groups in the polymer was 0.154 mol / 100 g by iodine titration, and the molecular weight by VPO was 3900.
Met. From the molecular weight and the number of moles of allyl groups determined by iodine titration, it was found that an average of about 6.0 allyl groups were introduced into one molecule of the polymer.

Synthesis Example 8 A 200-m four-necked flask equipped with a stirring rod, a dropping funnel, a thermometer, a three-way cock, and a condenser was prepared. Next, under a nitrogen atmosphere, the cyclic polysiloxane 9.26 g (38.5 mmol) (manufactured by Shin-Etsu Chemical Co., Ltd., LS 8600) and 20 m of toluene were charged in the flask. Allyl group-containing acrylate polymer 10g synthesized in Synthesis Example 7, chloroplatinic acid catalyst solvent chloride _{(H 2 PtCl 6 · 6H 2} O1g ethanol 1m
Solution in 9m of 1,2-dimethoxyethane) 16
A toluene solution of μ dissolved in 30 m of toluene was charged into the dropping funnel. The flask was heated to 70 ° C., and the toluene solution was dropped into the flask over 1 minute. After the completion of the dropwise addition, the reaction was further performed at 80 ° C. for 2 hours. At this time, when the remaining allyl group in the reaction solution was quantified by IR spectroscopy, it was confirmed that the carbon-carbon double bond at 1645 cm ^-1 had disappeared. Next, in order to remove the catalyst remaining in the reaction system, 2 g of silica gel (Wako Gel C-200 manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at room temperature for about 30 minutes, and then filtered using a flash column. . The filtrate was evaporated to remove toluene and excess cyclic polysiloxane, and further degassed under reduced pressure at 80 ° C. for 3 hours to obtain a colorless transparent viscous liquid. The hydrosilyl group in the acrylate polymer was confirmed as a strong absorption at 2150 cm ^{-1 in} the IR spectrum. The 300-MHz NMR spectrum shows Si-H
By comparing the intensity of the peak with the peak of the combination of Si—CH ₃ and Si—CH ₂ , it was found that an average of about 1.2 hydrosilyl groups reacted per molecule of the cyclic polysiloxane. That is, the polymer is a hydrosilyl group-containing acrylate polymer having a structure as shown in the following formula in which the molecular weight is partially increased by the cyclic hydrogen polysiloxane.

Examples 1 to 8 Using the polymers of Synthesis Examples 1 to 8, the chloroplatinic acid catalyst, and the silane coupling agent, compositions for adhesives were prepared according to the formulations shown in Table 1. The resulting composition was evaluated as an adhesive as follows. The results are shown in Table 1.

(1) Measurement of tensile shear strength and peel adhesive strength For the measurement of tensile shear strength, based on JIS K-6850, JIS H-4000 aluminum plate A-1050P (100 × 2
Using a (5 × 2 mm test piece), the compositions shown in Table 1 were applied with a spatula, then bonded together, and pressed by hand to prepare a test sample.

The peel adhesion strength was evaluated by a T-shaped peel test based on JIS K-6854. Aluminum plate A of JIS H-4000
A test sample was prepared by bonding the above deflecting parts using -1050P (a test piece of 200 × 25 × 0.1 mm) and pressing them five times using a 5 kg hand roller so as not to reciprocate in the length direction.

These test samples were cured by heating at 100 ° C. for 10 minutes and subjected to a tensile test. However, the pulling speed is
50mm / min for shear test, 200m for T-peel test
m / min.

(2) Curing test A part of the adhesive composition was placed on a gelling tester, and the snap-up time (time required to become a rubber elastic body) was measured at a predetermined temperature.

Comparative Example 1 Table 1 shows polypropylene oxide (molecular weight: 8000), both ends of which are blocked with a dimethoxysilyl group, a tin-based curing catalyst (U-220, manufactured by Nitto Kasei Co., Ltd.), and 3-aminopropyltrimethoxysilane. Example 1
The T-type peel strength and the shear strength were measured in the same manner as in Examples 8 to 8.
The results are shown in Table 1.

From Table 1, it was found that the composition for adhesives of the present invention is high-temperature and fast-curing.

[Effects of the Invention] According to the present invention, there is provided an adhesive composition which is rapidly curable and has excellent adhesiveness.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI C09J 183/05 C09J 183/05 183/10 183/10 (72) Inventor Koji Noda 6-21-21, Kodamayama, Tarumi-ku, Kobe-shi, Hyogo (72) ) Inventor Kazuya Yonezawa 5-12-11 Tsutsujigaoka, Tarumizu-ku, Kobe City, Hyogo Prefecture Referee, Yoshiaki Hanada Referee Yaichi Inoue Referee Noriko Suzuki (56) References JP-A-1-165681 (JP, A) JP JP-A-62-240361 (JP, A) JP-A-63-6041 (JP, A) JP-A-2-28280 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09J 4 / 00-4/06 C09J 101/00-201/10 C08F 299/00-299/08 C08G 77/00-77/62

Claims (3)

(57) [Claims] An adhesive composition comprising the following components (A) to (C): (A) in a molecule selected from the following formulas (II), (III), (IV) and (V) A compound having at least one alkenyl group (excluding an organopolysiloxane); (R ¹ is hydrogen or a methyl group, R ² is a divalent hydrocarbon group having 1 to 20 carbon atoms and may contain one or more ether bonds. R ³ is an aliphatic or aromatic organic group. , A is a positive integer.) A compound having an ether bond represented by the formula (III): (R ¹ is a hydrogen or methyl group, R ² is a divalent hydrocarbon group having 1 to 20 carbon atoms and may contain one or more ether bonds. R ⁴ is an aliphatic or aromatic organic group. , A is a positive integer.) A compound having an ester bond represented by the formula (IV): (R ¹ is hydrogen or a methyl group, R ⁵ is an aliphatic or aromatic organic group, and a is a positive integer.) A compound represented by the formula (V) (R ¹ is hydrogen or a methyl group, R ² is a divalent hydrocarbon group having 1 to 20 carbon atoms and may contain one or more ether bonds. R ⁶ is an aliphatic or aromatic organic group. , A is a positive integer.), (B) a compound having at least two hydrosilyl groups in a molecule, (C) a hydrosilylation catalyst. 2. The adhesive composition according to claim 1, further comprising a silane coupling agent. 3. The adhesive composition according to claim 1, wherein the component (A) is an alkenyl group-containing polyester having an average molecular weight of 500 to 50,000.