JP2866181B2 - Adhesive composition - Google Patents

Description

The present invention relates to a pressure-sensitive adhesive composition. More specifically, a compound having at least one alkenyl group in the molecule,
The present invention relates to a compound having at least two hydrosilyl groups in a molecule, and an addition-curable pressure-sensitive adhesive composition containing a hydrosilylation catalyst as a main component.

[Conventional technology and problems]

The pressure-sensitive adhesive is also called a pressure-sensitive adhesive and has a property of easily adhering to the surface of an object with a small pressure enough to be pressed with a fingertip. Such pressure-sensitive adhesives are used for pressure-sensitive adhesive products such as cellophane tapes, vinyl tapes for electrical insulation, masking tapes, pressure-sensitive adhesive sheets, and pressure-sensitive labels. In particular, an adhesive tape having a support made of polyvinyl chloride,
It is widely used because it has various excellent characteristics such as being inexpensive, having excellent water resistance and electric characteristics.

As the pressure-sensitive adhesive used for the pressure-sensitive adhesive tape, those mainly composed of natural rubber, synthetic rubber or the like, and those mainly composed of an acrylate copolymer are mainly used. However, these pressure-sensitive adhesive compositions are generally easily deteriorated by heat, light, etc., and when a pressure-sensitive adhesive product using the pressure-sensitive adhesive composition is used outdoors, the weather resistance is insufficient, so that terminal peeling or the like is likely to occur. As a result, the function as an adhesive product cannot be sufficiently achieved. In order to solve this problem, 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, and an adhesive Pressure-sensitive adhesive compositions containing an imparting resin have been developed (Japanese Patent Laid-Open No. 1-106868).
1).

However, since this pressure-sensitive adhesive composition is cured by a condensation reaction of a functional silyl group, there is a problem that the curing speed is slow, which is inconvenient for line production.

[Means for solving the problem]

The present invention has been made to solve the above problems, and includes a pressure-sensitive adhesive composition containing the following components (A) to (D) as main components.

(A) a compound having at least one alkenyl group in a molecule; (B) a compound having at least two hydrosilyl groups in a molecule; (C) a hydrosilylation catalyst; and (D) a tackifying resin.

The compound having at least one alkenyl group in the molecule, which is the component (A) of the present invention, is not particularly limited, and 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) (Wherein R ¹ is hydrogen or a methyl group).

When the component (A) is specifically described, first, the formula (II) (R ¹ is hydrogen or methyl, 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. In particular, 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, And the like. 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-based polymers, ethylene-propylene-based copolymers, polycondensates obtained by condensation of a dibasic acid such as adipic acid with glycol, or ring-opening polymerization of lactones. Isobutylene, copolymer of isobutylene with isoprene, polychloroprene, polyisoprene, copolymer of isoprene with butadiene, acrylonitrile, styrene, etc., copolymer of polybutadiene, butadiene with styrene, acrylonitrile, etc., polyisoprene, polybutadiene A polyolefin polymer obtained by hydrogenating a copolymer of isoprene or butadiene with acrylonitrile, styrene, etc .; a polyacrylic ester obtained by radical polymerization of monomers such as ethyl acrylate and butyl acrylate; Acrylates such as butyl acrylate, and vinyl acetate, acrylonitrile, methyl methacrylate, acrylate copolymers with styrene and the like, a graft polymer obtained by polymerizing a vinyl monomer in the organic polymer, Polysulfide polymer,
Nylon 6 by ring-opening polymerization of ε-caprolactam, Nylon 66 by condensation polymerization of hexamethylenediamine and adipic acid, Nylon 610 by condensation polymerization of hexamethylenediamine and sebacic acid, Nylon 11 by condensation polymerization of ε-aminoundecanoic acid, ε Nylon 12 by ring-opening polymerization of aminolaurolactam, polyamide polymer such as copolymer nylon having two or more components among the above-mentioned nylons, for example, polycarbonate produced by condensation polymerization of bisphenol A and carbonyl chloride Polymers, diallyl phthalate polymers and the like.

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, And the like. Of these, the following are preferred.

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.

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.

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.).

Wherein R ² is the same as R ² in formula (II).

In addition, as R ⁶ is, And the like. Of these, the following are particularly preferred.

R ⁶ may be an organic polymer, and all the organic polymers exemplified in the description of the formula (II) can be suitably used.

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 broadly divided.

Examples of a method for introducing an alkenyl group after polymerization include, for example, a polymer having a functional group such as a hydroxyl group or an alkoxide group at a terminal, a main chain or a side chain, an active group having reactivity with the above functional group, and an alkenyl group. An alkenyl group can be introduced into the terminal, main chain or side chain by reacting an organic compound having a group. 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,
Allyl chloroformate, allyl bromoformate, etc.
Unsaturated fatty acid substituted carbonic halide C ₃ -C _20, 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) 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 radical monomer such as a vinyl monomer having a low radical reactivity alkenyl group in a molecule such as allyl methacrylate or allyl acrylate, or a radical chain such as allyl mercaptan. By using a 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 length is longer at the molecular terminal because it is longer at the molecular terminal. preferable.

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. However, if a group containing a hydrosilyl group is specifically exemplified, then -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 = 1~3), -
SiH ₂ (C ₆ H ₁₃₎ hydrosilyl group containing only one silicon atom, such _{as, -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 a group selected from H, OSi (CH ₃ ) ₃ and an organic group having 1 to 10 carbon atoms, 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 integer, n is 0 or a positive integer, and 2 ≦ m + n ≦ 50). And groups derived from siloxane.

Among the above various hydrosilyl groups, the molecular weight of the group constituting the hydrosilyl group is desirably 500 or less from the viewpoint that the hydrosilyl group-containing compound of the present invention is less likely to impair the compatibility with the component (A). 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 group-containing 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. On the other hand, 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, the formula (VI) (Wherein, X is a group having at least one hydrosilyl group of the, R ^1, R ^2, R ³ may be used respectively R ^1, R ^2, R ³ in formula (II) the same. A compound having an ether bond represented by the formula: (Wherein, X is a group having at least one hydrosilyl group of the, R ^1, R ^2, R ⁴ may be used respectively R ^1, R ^2, R ⁴ in formula (III) the same. A compound having an ester bond represented by formula (VIII): (Wherein, X is a group having at least one hydrosilyl group of the, R ^1, R ⁵ has the formula (respectively R ^1, R ⁵ in IV) may be the same as.) Carbide represented by A hydrogen compound, and a compound of formula (IX) (Wherein, X is a group having at least one hydrosilyl group of the, R ^1, R ^2, R ⁶ can be used respectively R ^1, R ^2, R ⁶ in the formula (V) the same. 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 any polymer having a molecular weight of 500 to 50,000 can be suitably used, but one having a molecular weight of 500 to 20,000 is particularly preferable. 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 produced 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
Method of reducing of Si-Cl groups in the compound to Si-H groups of the organic compound having a group by treatment with a reducing agent such as LiAlH _4, NaBH _4,
(Ii) a method of reacting an organic compound having a functional group X in a molecule with a compound having a functional group Y and a hydrosilyl group simultaneously reacting with the functional group in the molecule, and (iii) an organic compound having an alkenyl group. Alternatively, a method may be considered in which a polyhydrosilane compound having at least two hydrosilyl groups is subjected to selective hydrosilylation, so that the hydrosilyl group remains in the molecule of the compound even after the reaction.
Of 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)
One or both of the components is preferably an organic polymer, and among them, a polypropylene oxide polymer is preferred.

When both the component (A) and the component (B) are low molecular weight compounds, the crosslinked density of the obtained cured product is increased and the viscosity is reduced, which is not preferable as a pressure-sensitive 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 ) (formula Wherein Me is a methyl group, Bu is a butyl group, Vi is a vinyl group, Ph is a phenyl group, and m and n are integers), dicarbonyldichloroplatinum, and US Pat. No. 3,159,601 to Ashby. Platinum-hydrocarbon complexes described in US Pat. No. 3,159,662, and US Pat. No. 32209 to Lamoreaux
Also included are the platinum alcoholate catalysts described in US Pat. In addition, Modic US Patent 351
The platinum chloride-olefin complex described in 6946 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, PdC
l 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 it is less than 10 ^-8 mol, curing does not proceed sufficiently. Further, the hydrosilylation catalyst is generally expensive and corrosive, and it is better not to use the hydrosilylation catalyst in an amount of more than 10 ^-1 mol since a large amount of hydrogen gas is generated and a cured product may foam.

In the present invention, since the pressure-sensitive 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, which is advantageous for performing line production.

The tackifier resin as the component (D) of the present invention is not particularly limited, and a commonly used resin can be used. Specific examples include phenol resins, modified phenol resins (eg, cashew oil-modified phenol resins, tall oil-modified phenol resins, etc.), terpene phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, xylene resins, petroleum resins, phenols Modified petroleum resin, rosin ester resin, low molecular weight polystyrene resin, terpene resin and the like can be mentioned. These may be used alone or in combination of two or more.

The amount of the tackifying resin used is 10 to 140 parts by weight, preferably 15 to 140 parts by weight based on 100 parts by weight of the total of the components (A) and (B).
80 parts by weight are preferred.

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 period or if moisture is mixed in, conversion of Si—H groups into Si—OH 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 selected arbitrarily as long as it is uniformly dispersed in the components (A) and (B).
10 ^-6 to 10 ^-1 mol per ¹ mol of Si-H group-containing compound as a component
It is preferable to use within the range. This is less than 10 ^-6 mol not improved sufficiently storage stability of component (B), 10 ^-1
This is because if it exceeds mol, curing is inhibited. The storage stability improvers may be used alone or as a mixture of two or more.

The composition of the present invention may further contain, if necessary, a nitrogen-containing silane compound, a plasticizer or a softener, a filler, an oxidizer, for improving the adhesion to various supports (plastic film, metal foil, paper, etc.). An inhibitor, an ultraviolet absorber, a pigment, a surfactant, a solvent, a silicon compound, and the like may be appropriately added.

Specific examples of the nitrogen-containing silane compound include, for example, H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , H ₂ NCH ₂ CH ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , H ₂ NCH ₂ CH ₂ NCH 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 and H _{5) 3,} amino and / or imino group-containing alkoxysilane and the like, the amino group and / or imino group-containing alkoxysilane, Reaction product with an epoxysilane compound such as the above, the amino group and / or imino group-containing alkoxysilane and CH ₂ ＣC (CH ₃ ) COOCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CH ₂ ＣC ( CH ₃ ) COOCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₂ OCH ₃ ) ₃ and a reaction product with a methacryloxysilane compound.

The amount of the nitrogen-containing silane compound to be used is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the total of the components (A) and (B).

Specific examples of the plasticizer and the softener include, for example, dioctyl phthalate, butylbenzyl phthalate, polypropylene glycol, chlorinated paraffin, liquid polybutadiene, and the like.

Specific examples of the filler include, for example, silica fine powder,
Examples thereof include calcium carbonate, clay, talc, titanium oxide, zinc white, diatomaceous earth, barium sulfate, and carbon black. Among these fillers, silica fine powders, particularly, having a particle diameter of 70 to 50 nm (BET specific surface area of 50 to 3
Fine powdered silica of about 80 m ² / g) is preferred, and among them, hydrophobic silica subjected to surface treatment is particularly preferred because it has a large effect of improving strength in a preferred direction.

〔Example〕

Next, the composition of the present invention will be specifically described by way of examples, but the present invention is not limited to only these examples.

Synthesis Example 1 According to the method disclosed in JP-A-53-134095, polyoxypropylene having an allylic olefin group at the 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 200 ml four-necked flask was equipped with a cooling tube with a three-way cock.
A device equipped with an equalizing dropping funnel, a thermometer, a magnetic chip, and a glass stopper was prepared. Cyclic polyhydrogensiloxane under N ₂ 12.03 g (50 mmol) (LS-8600, manufactured by Shin-Etsu Chemical Co., Ltd.) and 20 ml of toluene were charged in a flask. 1,9-decadiene 2.76 g (20 mmol), chloroplatinic acid catalyst solution (H ₂ PtCl ₆ · 6H
The ₂ O 1 g ethanol 1 g, 1,2-dimethoxy solution was dissolved in ethane 9 g) 20 [mu] was charged into the dropping funnel which was dissolved in toluene 30 ml. The flask was placed in a 50 ° C. oil bath, and the toluene solution was dropped into the flask over 2 hours under a N ₂ atmosphere. At the time when the reaction was further carried out at 50 ° C. for 1 hour after the completion of the dropping, the 1R spectrum was measured to be
^The reaction was terminated at this point because the absorption of olefin near ^-1 had completely disappeared. The toluene solution after the completion of the reaction was washed with a saturated aqueous solution of ammonium chloride (100 ml × 2) and exchanged water (100 ml × 1), and then dried over Na ₂ SO ₄ . Na ₂ SO
₄ was removed by filtration, and benzothiazole (13 μ, 0.1
2 mmol), and after removing volatiles by evaporation, 80
Degassed under reduced pressure at ℃ to obtain 9.11 g of colorless and transparent liquid. The hydrosilyl group in the hydrocarbon compound is 2170 cm
It was confirmed as a strong absorption of ^-1 . In addition, 300MHz NMR
By comparing the calculated intensity ratio with the proton intensity ratio (actually measured value 0.216) between the peak of H and Si—C H ₃ , the compound has, on average, a structure of the following formula [n = 1 (MW =
998) was 53% and n = 2 (MW = 1377) was 47%]. Based on this, the number of Si—H groups in the unit weight was calculated to be 0.769 mol / 100 g.

Synthesis Example 3 114 g (0.5 mol) of bisphenol A, 250 ml (1.25 mol) of a 5N aqueous sodium hydroxide solution and 575 ml of ion-exchanged water were mixed well. Next, benzyltriethylammonium chloride is used as a phase transfer catalyst. Was added. 242 g (2.0 mol) of allyl bromide in the aqueous solution
Was dissolved in 300 ml of toluene, and the solution was gradually dropped from a dropping funnel. The reaction was carried out with stirring at 80 ° C. for 2 hours.
At this time, the pH of the aqueous layer was measured and found to be acidic, so the heating and stirring were stopped. After washing the organic layer with layer water, further washed with deionized water and dried with NaSO _4. After removing volatile matter by evaporation, the residue was dried under reduced pressure at 80 ° C. for 2 hours to obtain 146 g (yield 95%) of a pale yellow viscous liquid. The viscous liquid was identified as diallyl ether of bisphenol A by elemental analysis, 300 MNz ¹ H NMR, identification by IR spectrum and the like.

IR (neat) cm ^-1 , 3070 (M, ν = CH), 3030 (m), 296
0 (S), 2920 (S), (νC-H), 1645 (m, νC-
H), 1620 (S), 1520 (S), 1290 (S), 1235 (S), 1
180 (S), 1025 (S), 1000 (S), 920 (S), 825
(S) Elemental analysis, calculated value C, 81.78%; H, 7.84% Actual value C, 81.9%; H, 7.96% Synthesis Example 4 200 ml equipped with a stirring rod, a dropping funnel, a thermometer, a three-way cock, and a cooling tube. Was prepared. Next, under a nitrogen atmosphere, cyclic hydrogen polysiloxane 12.03 g (50 mmol) (LS-8600, manufactured by Shin-Etsu Chemical Co., Ltd.) and 20 ml of toluene were charged in a flask. 6.16 g (20 mmo) of bisphenol A diallyl ether synthesized in Synthesis Example 3
l), 41 μl of chloroplatinic acid catalyst solvent solution (1.0 g of H ₂ PtCl ₆ · GH ₂ O dissolved in 9 g of ethanol / 1,2-dimethoxyethane (1/9 V / V)) dissolved in 50 lm of toluene After mixing well, the mixture was charged into a dropping funnel. At 70 ° C., the toluene solution was dropped into the flask over 1.5 hours. At the time when the reaction was further carried out at 80 ° C. for 5 hours, an IR spectrum was taken. Since the absorption derived from the olefin at 1645 cm ⁻¹ had completely disappeared, the reaction was terminated at this point. Dimethyl acetylenedicarboxylate (34μ, 0.24
mmol), and the toluene was distilled off under reduced pressure.
After drying under reduced pressure for 1 hour, 12.0 g of a pale yellow viscous liquid was obtained. This viscous liquid was found to be a Si—H-containing ether compound having the following structural formula by identification of 300 MHz ¹ H NMR, IR spectrum and the like.

Synthesis Example 5 A 200 ml four-necked flask was equipped with a cooling tube with a three-way cock.
A device equipped with an equalizing dropping funnel, a thermometer, a rotor, and a glass stopper was prepared. Under nitrogen atmosphere, cyclic polyhydrogensiloxane 12.03 g (50 mmol) (LS-8600, manufactured by Shin-Etsu Chemical Co., Ltd.) and 20 ml of toluene were charged in a flask. Diethylene glycol diallyl carbonate (RAV-7N, manufactured by Mitsui Petrochemical Co., Ltd.) 5.49 g (20 mmol),
Chloroplatinic acid catalyst solution chloride _{(H 2 PtCl 6 · 6H 2} O 1.0g Ethanol
A solution prepared by dissolving 41 μm of / 1,2-dimethoxyethane (9 g in 1/9 V / V) in 50 ml of toluene was charged into a dropping funnel. Put the flask in a 50 ° C oil bath,
The toluene solution was dropped into the flask over 1.5 hours under a nitrogen atmosphere. When the IR spectrum was measured after the completion of the dropwise addition, the absorption of the olefin near 1640 cm ^-1 had completely disappeared. At this point, the stirring was stopped. Dimethyl acetylenedicarboxylate (34μ,
After adding 0.24 mmol), the mixture was evaporated to remove volatile components, thereby obtaining 10.2 g of a slightly viscous pale yellow liquid. The hydrosilyl group of the carbonate compound was confirmed as a strong absorption at 2170 cm ^{-1 in} the IR spectrum. Also 30
By comparing the Si- intensity ratio of protons between the peak and the Si-C H ₃ of H (measured value 0.181) and the intensity ratio of the calculated at 0MHz of NMR, the compound has the structure of formula average I understand. Based on this, the number of Si—H groups in the unit weight was calculated to be 0.47 mol / 100 g.

Synthesis Example 6 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, 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
% Is allyl group polypropylene oxide 300 g (moles 0.069mol allyl group), toluene 230 ml, and chloroplatinic acid catalyst solvent solution _{(H 2 PtCl 6 · 6H 2} O 1.0g ethanol /
1,2-dimethoxyethane (1/9 V / V) dissolved in 9G)
A toluene solution of 83 μ was charged into the dropping funnel.
The flask was heated to 70 ° C. and the toluene solution was
It was dropped at a rate of 2 ml over 5 hours. Thereafter, the reaction temperature was increased to 8
When the temperature was raised to 0 ° C. and the mixture was stirred for about 6 hours, the remaining allyl groups in the reaction solution were quantified by IR spectroscopy, and it was confirmed that the carbon-carbon double bond at 1645 cm ⁻¹ had disappeared. . After adding dimethyl acetylenedicarboxylate (118 μm, 0.83 mmol) to the reaction mixture, degassing was performed under reduced pressure at 80 ° C. for 3 hours to remove toluene and unreacted excess cyclic polysiloxane in the reaction system. About 315 g of polypropylene oxide having a group,
Obtained as a pale yellow, viscous liquid. The viscosity measured by an E-type viscometer was 310 poise (40 ° C.). The hydrosilyl group in the polypropylene oxide was 2150 cm ^{-1 in the} IR spectrum.
As strong absorption. By analyzing the NMR spectrum at 300 MHz and comparing the peak intensity of the combined Si— CH ₃ and Si— CH ₃ — with the peak intensity of Si— H, an average of 1.31 per molecule of the cyclic polysiloxane was obtained. It was found that two hydrosilyl groups had reacted. That is, the polymer is a polypropylene oxide having a molecular terminal represented by the following formula, in which the molecular weight has been increased by one part by the cyclic hydrogen polysiloxane.

Examples 1 to 12 The organic polymer obtained in Synthesis Example 1, the Si-H group-containing compound obtained in Synthesis Examples 2, 4, 5, or 6, a tackifier resin [terpene-phenol resin (Yasuhara Yushi Co., Ltd.) Product name: Y
S Polystar T-115)], a hindered phenol antioxidant (manufactured by Ciba-Geigy Irganox 1010), and chloroplatinic acid catalyst solution _{(H 2 PtCl 6 · 6H 2} O 1.0g Ethanol
/ 1,2-Dimethoxyethane (dissolved in 99 g of 1/9 V / V) was weighed as shown in Table 1, mixed well, and then defoamed under reduced pressure. The thickness after drying the obtained pressure-sensitive adhesive composition is 25μ.
m was applied to a 25 μm-thick polyester film and cured at 100 ° C. for 2 minutes to produce an adhesive tape.

Paste the obtained adhesive tape on a stainless steel plate,
After standing for 60 minutes, a 180 ° peel test was performed at 23 ° C. at a peel speed of 200 mm / min, and the force required for peeling was measured. The results are shown in Table 1.

In addition, a part of the composition for pressure-sensitive adhesive was placed on a gelling tester, and a snap-up time (time until a rubber elastic body was formed) was measured at a predetermined temperature. The results are shown in Table 1. From Table 1, it was found that the composition for a pressure-sensitive adhesive of the present invention was high-temperature and fast-curing.

Examples 13 to 15 A pressure-sensitive adhesive composition was prepared in the same manner as in Examples 1 to 12 except that 1,9-decadiene and the Si-H group-containing polymer of Synthesis Example 6 were used. Was measured. The snap-up time of the pressure-sensitive adhesive composition was measured in the same manner.
The results are shown in Table 1.

Examples 16 to 18 Examples 1 to 12 except that the diallyl bisphenol A produced in Synthesis Example 3 and the Si-H group-containing polymer of Synthesis Example 6 were used.
A pressure-sensitive adhesive composition was prepared in the same manner as in the above case, and its 180 ° peel strength was measured. The snap-up time of the pressure-sensitive adhesive composition was measured in the same manner. The results are shown in Table 1.

Comparative Examples 1 to 3 Polypropylene oxide (molecular weight: 8000) having both ends blocked with a dimethoxymethylsilyl group, a tackifier resin [terpene-phenol resin (manufactured by Yasuhara Resin Co., Ltd., trade name: Y
S-Polystar T-115)], a hindered phenolic antioxidant (Irganox 1010 manufactured by Ciba Geigy), and a curing catalyst (dibutyltin-based, U-22 manufactured by Nitto Kasei Co., Ltd.)
0) were mixed in the proportions shown in Table 1. Using the obtained pressure-sensitive adhesive composition, a pressure-sensitive adhesive was prepared in the same manner as described above, and its 180 ° peel strength was measured. The snap-up time of the pressure-sensitive adhesive composition was measured in the same manner. The results are shown in Table 1.

[Action and Effect] As described above, the pressure-sensitive adhesive composition of the present invention has a high curing rate and is suitable for line production.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Kazuya Yonezawa 5-12-11 Tsutsujigaoka, Tarumizu-ku, Kobe-shi, Hyogo (56) References JP-A-62-240361 (JP, A) (58) Fields studied (Int .Cl. ⁶ , DB name) C09J 4/00-4/06, 7/00-7/04 C09J 101/00-201/10

Claims (1)

(57) [Claims] 1. An adhesive composition comprising the following components (A) to (D) as main components: (A) a compound having at least one alkenyl group in a molecule; and (B) at least two compounds in a molecule. (C) a hydrosilylation catalyst, and (D) a tackifier resin.