JP2938943B2 - Pressure sensitive adhesive - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a pressure-sensitive adhesive layer laminated on a base material having both flexibility and high tensile strength obtained by curing a specific composition. High adhesive strength (shear adhesive strength and peel adhesive strength)
The present invention relates to a tape-shaped or sheet-shaped pressure-sensitive adhesive having:

[Conventional technology and problems]

Conventionally, several methods for obtaining a tape or sheet-shaped pressure-sensitive adhesive having a relatively high adhesive force are known.

For example, as a method of obtaining a pressure-sensitive adhesive having a relatively high adhesive strength, a method of thickening a pressure-sensitive adhesive layer is known.
Since the thickness of the pressure-sensitive adhesive layer is limited as long as the pressure-sensitive adhesive layer is formed by using a solvent-type or emulsion-type pressure-sensitive adhesive, the adhesive strength is also limited.

In addition, when a thick foam is used as the base material, the adhesiveness of the pressure-sensitive adhesive becomes relatively good, but in the case of the most common urethane foam or polyethylene foam, a relatively high shear adhesive force is obtained. Then, the peel adhesive strength becomes insufficient, and if it has a relatively high peel adhesive strength, there is a limit in the shear adhesive strength as a pressure-sensitive adhesive, and the relatively high peel adhesive strength and the relatively high shear adhesive strength are combined. There is a problem that it is not easy to give, and satisfactory characteristics are not obtained.

In order to solve such a problem, a pressure-sensitive adhesive film containing a specific kind of air bubbles at a specific ratio has been produced, and a pressure-sensitive adhesive having both flexibility and relatively high adhesive strength has been obtained (see, for example, Japanese Patent Application Laid-Open No. H11-157556). JP-A-58-125776). However, this pressure-sensitive adhesive is a special material containing a specific type of air bubbles at a specific ratio, and is different from the usual method, that is, after foaming a composition which becomes a pressure-sensitive adhesive state when polymerized, the base is obtained. The drawback is that it must be placed on a material and polymerized on site before the bubbles of the foam do not disappear so as to have a pressure-sensitive adhesive property. There is.

In addition, pressure-sensitive adhesive tapes containing glass micro-bulbs instead of the above-mentioned air bubbles have been studied.
53-141346 and 62-34976), the fact is that bubbles are easily broken at the time of mixing, and care must be taken in handling.

In order to solve these problems, a pressure-sensitive adhesive layer is laminated on both surfaces of a substrate obtained by curing a liquid rubber-based organic polymer at room temperature having at least one reactive silicon in a molecule. Pressure-sensitive adhesives have been developed (see
-28277). However, the curing of the base portion of the pressure-sensitive adhesive requires a relatively long time at a relatively high temperature, and the line productivity is low.
In addition, there is a problem that the peeling adhesive strength decreases with time.

[Means for solving the problem]

An object of the present invention is to overcome these problems and to obtain a pressure-sensitive adhesive in which the base material is fast-curing, has flexibility and relatively high adhesive strength, and does not decrease peel adhesion strength. It was done as.

That is, the first aspect of the present invention is to laminate a pressure-sensitive adhesive layer on a substrate obtained by crosslinking and curing a curable composition containing the following components (A) to (C) as main components. (A) an organic polymer containing at least one alkenyl group in a molecule, (B) an organic compound containing at least two hydrosilyl groups in a molecule, (C) a hydrosilylation catalyst, A second aspect of the present invention is a photosensitive composition obtained by laminating a pressure-sensitive adhesive layer on a substrate obtained by crosslinking and curing a curable composition containing the following components (A) to (D) as main components. (A) an organic polymer containing at least one alkenyl group in the molecule, (B) an organic compound containing at least two hydrosilyl groups in the molecule, (C) a hydrosilylation catalyst, (D) ) A storage stability improver shall be included in each content.

The base portion of the pressure-sensitive adhesive according to the first aspect of the present invention is produced by crosslinking and curing a composition comprising the following three components.

(A) an organic polymer containing at least one alkenyl group in a molecule; (B) an organic compound containing at least two hydrosilyl groups in a molecule; (C) a hydrosilylation catalyst.

The base portion of the pressure-sensitive adhesive according to the second aspect of the present invention comprises four components obtained by further adding a storage stability improver as a component (D) to the three components (A) to (C). It is produced by crosslinking and curing the composition.

The base portion can be prepared using other compounds, for example, a hydroxyl group as a reactive group in the molecule,
Curing a liquid organic polymer at room temperature having at least one isocyanate group, glycidyl group, acryloyl group, methacryloyl group, amino group, amide group, carboxyl group, mercapto group in the presence or absence of a crosslinking curing agent Methods and the like may be mentioned, but from the viewpoint of high curing speed and flexibility after curing, the above (A) to (D)
It is preferred to use a composition comprising the components.

The main chain of the organic polymer containing at least one alkenyl group in the molecule (A) is not particularly limited as long as the cured product is an organic polymer that becomes a rubbery substance. Polyethers having a repeating unit whose main chain is essentially represented by the general formula: -RO- (wherein R is a divalent organic group) as described in JP-A-62-335798. 59
As described in JP-168014, such as 2-ethylhexyl acrylate, polyacrylates obtained by radical polymerization of acrylates such as butyl acrylate, and acrylates such as 2-ethylhexyl acrylate and butyl acrylate and vinyl acetate, Acrylate copolymers with acrylonitrile, methyl methacrylate, styrene, etc .: Japanese Patent Application No. 62-327938
Hydrocarbons such as isobutylene-based polymers and hydrogenated polydiene-based polymers as described in the specification of Japanese Patent Application No. 62-330890, etc .: cyclic ethers such as polypropylene oxide, ethylene oxide and tetrahydrofuran; C 1 in the polyether polymer obtained by polymerization
And vinyl polymer-modified polyether-based polymers obtained by polymerizing vinyl monomers such as acrylic acid esters and methacrylic acid esters of alcohols Nos. To 12, vinyl acetate, acrylonitrile, and styrene.

Among these, in the polymer, a repeating unit represented by the general formula: -RO- is more than 50% (% by weight, the same applies hereinafter),
A polyether polymer containing 70% or more, more preferably 90% or more is preferable, and a polypropylene oxide polymer is particularly preferable.

The alkenyl group is not particularly limited, but may have the formula (I) (Wherein, R ¹ is hydrogen or a methyl group).

About the method of introducing an alkenyl group into the polymer,
Although various proposals can be used, they can be broadly classified into a method of introducing an alkenyl group after polymerization and a method of introducing an alkenyl group during polymerization.

As a method for introducing an alkenyl group after polymerization, for example, an organic group having a functional group such as a hydroxyl group or an alkoxide group at a terminal, main chain or side chain, an active group and an alkenyl group reactive with the above functional group An alkenyl group can be introduced into the terminal, main chain or side chain by reacting an organic compound having Examples of the organic compound having an active group and an alkenyl group having reactivity to the functional group include acrylic acid, methacrylic acid, vinyl acetic acid, acrylic acid chloride, acrylic bromide, and the like.
C unsaturated fatty ₃ -C _20, acid halides, acid anhydrides or allyl chloroformate _{(CH 2 = CHCH 2 OCOCl)} , C 3 -C 20 , such as allyl bromo formate (CH ₂ = CHCH ₂ OCOBr) Unsaturated fatty acid-substituted carbonate halide, allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl (chloromethyl) ether, allyl (chloromethoxy) benzene, Butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy) benzene, allyloxy (chloromethyl) benzene and the like.

As a method for introducing an alkenyl group during polymerization, for example, when the organic polymer of the present invention is produced by a radical polymerization method, vinyl monomers having an alkenyl group having a low radical reactivity in a molecule such as allyl methacrylate and allyl acrylate By using a radical chain transfer agent having an alkenyl group having low radical reactivity such as allyl mercaptan, an alkenyl group can be introduced into the main chain or terminal of the polymer.

The alkenyl group-containing organic polymer as the component (A) may be linear or branched, and any 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 of the component (A) may be present at the molecular terminal or in the molecule. However, when a rubber-like cured product is produced using the composition of the present invention, the effective network is preferably located at the molecular terminal. It is preferable because the chain length becomes long.

The organic compound containing 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, it can be represented by -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), -
Hydrosilyl group containing only one silicon base paper such as SiH ₂ (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 or more 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 ≦ 5
0) (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) Various chain, branched, and cyclic polyvalent hydrogensiloxanes represented by, for example, And groups derived therefrom.

Among the above-mentioned various hydrosilyl-containing groups, the molecular weight of the part of the group constituting the hydrosilyl group is small in that the compatibility of the hydrosilyl group-containing organic curing agent of the present invention with various organic polymers is unlikely to be impaired. 500 or less is desirable, further considering the reactivity of the hydrosilyl group,
The following are preferred.

When two or more groups having a hydrosilyl group are present in the same molecule, they may be the same or different.

The total number of hydrosilyl groups contained in the component (B) should be at least two in one molecule, but is preferably 2 to 15, more preferably 3 to 12. When the hydrosilyl group-containing organic compound of the present invention is mixed with various organic polymers containing an alkenyl group in the presence of a hydrosilylation catalyst and cured by a hydrosilylation reaction, when the number of the hydrosilyl groups is less than 2, The curing is slow and often causes poor curing. When the number of the hydrosilyl groups is more than 15, the stability of the curing agent 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 is represented by the general formula (II) X—R ² — (II) (X is a substituent containing at least one hydrosilyl group,
R ² is a divalent hydrocarbon group having 2 to 20 carbon atoms and may contain one or more ether bonds.)

The component (B) has a hydrosilyl group bonded to the organic component of the main chain in the form represented by the formula (II). The main chain skeleton is not particularly limited, and the organic polymer may be a low molecular weight compound. Various types can be used.

As the organic polymer, all the polymers listed as the component (A) can be suitably used. Among them, 50% or more of the repeating unit represented by the general formula: -RO-
A polyether polymer having preferably 70% or more, more preferably 90% or more is preferable, and a polypropylene oxide polymer is particularly preferable.

Although various compounds can be used as the low molecular weight compound, specifically, first, the compound represented by the formula (III) (X—R ² —O) _a R ³ (III) (X and R ² are the same as above) , R ³ is an organic group having 1 to 30 carbon atoms, a is 1
An integer selected from ~ 4. And a compound having an ether bond represented by the formula:

In the formula (III), R ² represents a divalent hydrocarbon group having 2 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 O-CH 2} CH 2 -, - CH 2 CH 2 O-CH 2 CH 2 CH 2 - and the like. -CH ₂ CH ₂ CH _2-
Is preferred.

In the formula (III), R ³ is an aromatic or aliphatic monovalent to tetravalent organic group having 1 to 30 carbon atoms. Specifically,
CH ₃ −, CH ₃ CH ₂ −, CH ₃ CH ₂ CH ₂ −, And the like. Of these, the following are preferred.

Next, the general formula (IV) (X is a group containing at least one hydrosilyl group, R ² is a divalent hydrocarbon group having 2 to 20 carbon atoms and may contain one or more ether bonds. R ⁴ has 1 to 2 carbon atoms. And an organic group of 30 and a is an integer selected from 1 to 4.).

In the formula (IV), R ² is the same as R ² in the formula (III).

R ⁴ is an aromatic or aliphatic 1 to 30 carbon atoms.
It is a tetravalent organic group. Specifically, CH ₃ −, CH ₃ C
H ₂ −, CH ₃ CH ₂ CH ₂ −, − (CH ₂ ) ₂ −, − (CH ₂ ) ₃ − −
(CH ₂ ) ₄ -,-(CH ₂ ) ₅ -,-(CH ₂ ) ₆ -,-(C
H ₂ ) ₇ −, And the like. Of these, the following are preferred.

-(CH ₂ ) ₂ -,-(CH ₂ ) ₃ -,-(CH ₂ ) _6- , Next, the general formula (V) X _a -R ⁵ (V) (X is a group containing at least one hydrosilyl group, R ⁵ is a monovalent to tetravalent hydrocarbon group having 2 to 50 carbon atoms, and a is 1 And an integer selected from the group consisting of a hydrocarbon having a main chain skeleton represented by the following formula:

In the formula (V), R ⁵ represents a monovalent to tetravalent hydrocarbon group having 2 to 50 carbon atoms. − (CH ₂ ) _n − (n = 2 to 10), And the like.

Of these,-(CH ₂ ) _n- (n = 2 to 10), Is preferred.

Further, — (CH ₂ ) _n — (n = 2 to 10) is particularly preferred.

Specific examples of the component (B) further include a compound represented by the general formula (VI): (X is a group containing at least one hydrosilyl group, R ² is a divalent hydrocarbon group having 2 to 20 carbon atoms and may contain one or more ether bonds. R ⁶ has 1 to 4 valences. An organic group of a
Is an integer selected from 1 to 4. And a compound having a carbonate bond represented by the formula:

Wherein, R ² is Formula (III), the same as R ² in (IV). Also R ⁶
Are 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 1 to 5) An integer of 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 − The hydrosilyl group-containing compound as the component (B) has a molar ratio of the hydrosilyl group to the alkenyl group as the component (A) of 0.2.
It is preferable to use it in the range of 5.05.0. If the molar ratio is less than 0.2, poor curing will occur, and if it is greater than 5.0, mechanical properties after curing will decrease.

The method for producing the hydrosilyl group-containing organic compound of the present invention is not particularly limited, and any method may be used.
For example, (i) an organic compound having a Si-Cl group in a molecule is Li
Treatment with a reducing agent such as AlH ₄ , NaBH _4, etc.
(Ii) a method in which an organic compound having a functional group X in a molecule is reacted with a compound having a functional group Y and a hydrosilyl group which react with the above functional group in the molecule. (Iii) a method of selectively hydrosilylating a polyhydrosilane compound having at least two hydrosilyl groups with respect to an organic compound containing an alkenyl group so that the hydrosilyl group remains in the molecule of the compound even after the reaction. Conceivable. (Iii) of these
Is particularly preferred. The hydrosilyl group-containing organic compound as the component (B) may be used alone or in combination of two or more.

Examples of the hydrosilylation catalyst which is the component (C) of the present invention include platinum alone, solid platinum supported on a carrier such as alumina, silica and carbon black, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde and 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 corrosive, and a large amount of hydrogen gas may be generated to cause a cured product to foam. Therefore, it is preferable not to use the hydrosilylation catalyst in an amount of 10 ^-1 mol or more.

When the hydrosilyl group-containing organic compound as the component (B) of the present invention is produced by the above-mentioned selective hydrosilylation,
Even after the reaction, since the component (B) contains a hydrosilylation catalyst, its stability is generally not good, and if it is left for a long period of time or if moisture is mixed in, the Si—H groups are converted to Si—OH groups. And phenomena such as viscosity increase and gelation are observed. Therefore, it is essential to include a storage stability improver as the component (D) in the component (B). Furthermore, this (D)
The components deactivate the hydrosilylation catalyst at low temperatures,
Since the hydrosilylation reaction is not hindered at a relatively high temperature, the composition of the present invention gives a cured product having excellent mechanical properties.

As the component (D), 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 favorably used.

Compounds containing an aliphatic unsaturated bond include compounds represented by the general formula (VI
I) (Wherein R ⁷ and R ⁸ are a hydrogen atom, an alkyl group, an aryl group, or R ⁷ and R ⁸ are interconnected at the other end) represented by the general formula (VIII) (Wherein R ⁹ , R ¹⁰ , and R ¹¹ are a hydrogen atom or a hydrocarbon group, and the total number of carbon atoms of R ⁹ , R ¹⁰ , and R ¹¹ is 2-6. When R ⁹ , R ¹⁰ and R ¹¹ are hydrocarbon groups, R ⁹ and R ¹⁰ or R ¹⁰ and R ¹¹ may be mutually connected at the other end.) ) Wherein R ¹² , R ¹³ and R ¹⁴ are a hydrocarbon group having 1 to 10 carbon atoms, provided that R ¹³ and R ¹⁴ may be mutually connected at the other end. ), General formula (X) (Wherein at least one of R ¹⁵ is a hydrocarbon group having an acetylenically unsaturated bond) represented by the general formula (XI) (Wherein, R ^{16 to} R ²⁰ are a hydrogen atom, a halogen or a monovalent hydrocarbon group, X is a halogen or an alkoxy group such as chlorine or bromine), a tetramethylvinylsiloxane cyclic, 2-pentene Nitrile, general formula (XI
I) (Wherein R ²¹ is a monovalent organic group containing at least one acetylene bond), an aliphatic carboxylic acid ester of an olefinic alcohol such as vinyl acetate,
Alkyl acetylenedicarboxylate represented by the general formula (XIII) R ²² O ₂ C—C≡C—CO ₂ R ²² (XIII) (wherein R ²² is a hydrocarbon group such as methyl and ethyl); X
IV) (Wherein R ²³ is methyl,
Hydrocarbon groups such as ethyl, allyl, and hydrocarbonoxyalkyl group), diorganofumarate and the like.

Triorganophosphine as an organic phosphorus compound,
Examples thereof include diorganophosphine, triorganophosphite, and organophosphonic acid.

Examples of the organic sulfur compound include organomercaptan, diorganosulfide, diorganosulfoxide, organosilanes containing a mercapto group, hydrogen sulfide, benzothiazole, benzothiazole disulfite, 2- (4-
(Morphodinyldithio) benzothiazole and the like.

Examples of the nitrogen-containing compound include ammonia, primary to tertiary alkylamine, arylamine, alkylarylamine, N, N-diorganoamino alcohol, urea, thiourea, pyrimidine, picoline, hydrazine, sulfonamide, benzotriazole, and quinoline. , triallyl isocyanurate, the general formula _{^{(XV) R 24 2 NR 26}} NR 25 2 (XV) a diamine compound represented by (wherein, R ²⁴ is an alkyl group containing from 1 to 4 carbon atoms, R ²⁵ is hydrogen Or R ²⁴ and R
²⁶ is an alkyl group containing 2 to 4 carbon atoms).

Stannous halide dihydrate as a tin compound,
Examples thereof include stannous carboxylate.

Examples of the organic peroxide include di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and 2,5-dimethyl-2,5-di (t-butyl). Tylperoxy) -3-hexyne, dicumyl peroxide, t
-Butylcumyl peroxide, dialkyl peroxides such as α, α'-bis (t-butylperoxy) isopropylbenzene, benzoyl peroxide, p-chlorobenzoyl peroxide, m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl Diacyl peroxides such as peroxides,
Peresters such as t-butyl perbenzoate, diisopropyl percarbonate, peroxydicarbonates such as di-2-ethylhexyl percarbonate, 1,1-di (t-butylperoxy) cyclohexane, 1,1- Examples thereof include peroxyketals such as di (t-butylperoxy) -3,3,5-trimethylcyclohexane.

Among them, dialkyl malate, dialkyl acetylenedicarboxylate, 2-pentennitrile, benzothiazole, quinoline, 2, 3-Dichloropropene is preferred. Further, 2-pentenenitrile benzothiazole and quinoline are particularly preferable, since the viscosity increase of the component (B) is almost completely suppressed even at a relatively high temperature (about 50 ° C.).

The amount of the component (D) can be selected almost arbitrarily as long as it is uniformly dispersed in the organic polymer of the component (A) and the component (B).
It is preferably used in the range of 10 ^-6 to 10 ^-1 mol per mol. This is because if it is less than 10 ^-6 mol, the storage stability of the component (B) is not sufficiently improved, and if it exceeds 10 ^-1 mol, curing is inhibited. The storage stability improvers may be used alone or in combination of two or more.

In the present invention, a composition obtained by crosslinking and curing a composition containing the above three or four components as a main component (hereinafter referred to as a “base material composition”) is used as a base material of the pressure-sensitive adhesive. . The crosslinking / curing reaction is extremely rapid since it proceeds by the addition reaction of the hydrosilyl group to the carbon-carbon double bond, which is convenient for line production of the base material. In addition, since the final gel fraction is high, the amount of transfer from the substrate portion to the pressure-sensitive adhesive layer after laminating the pressure-sensitive adhesive layer is quantitatively small, and the adhesive strength does not decrease.

The term “main component” means that the ratio of the active ingredient in the base material composition is 40% or more, preferably 50% or more. If the content is less than 40%, the curability becomes unstable, that is, the curing speed and the physical properties after curing tend to vary.

Examples of the components that can be used in addition to the three or four components that constitute the base material composition include, for example, a tackifier resin used to adjust the flexibility of the base material and to increase the strength,
Solvents that can be used to adjust the viscosity of the base material composition, silicon compounds that are used mainly to adjust the flexibility of the base material, and fillers that are used to adjust the physical properties of the base material And plasticizers and softeners, inorganic spherical micro hollow bodies for reducing the weight and cost of the substrate, and further include antioxidants, ultraviolet absorbers, pigments, surfactants, and the like, but are not limited thereto. Not something.

The tackifying resin is not particularly limited, and any commonly used tackifying resin can be used.

Specific examples of such tackifying resins include, for example, phenolic resins, modified phenolic resins (eg, cashew oil-modified phenolic resins, tall oil-modified phenolic resins, etc.), terpene-phenolic resins, xylene-phenolic resins, cyclopentadiene-phenolic resins. , Xylene resin, petroleum resin, phenol-modified petroleum resin, rosin ester resin, low molecular weight polystyrene resin, terpene resin and the like. These may be used alone,
You may mix and use 2 or more types. Among these, phenol resin-based and phenol-containing resin-based resins are particularly preferred because they easily exhibit flexibility, high elongation and high strength. Among the phenolic resin-based and phenol-containing resin-based resins, novolak resins are preferred because they have low reactivity and are easy to handle. Further, in the case of a novolak type phenolic resin, those having a softening temperature of 50 to 180 ° C are preferred.

The amount of the tackifying resin used is determined based on the amount of the organic polymer 10 (A).
0 to 10 parts by weight (the same applies hereinafter), 10 to 140 parts, and even 15
~ 80 parts are preferred. If the amount is less than 10 parts, the flexibility, elongation and strength of the obtained substrate will not be sufficiently improved, and if it exceeds 140 parts, a high elastic modulus will be obtained and rubber-like properties will not be sufficiently obtained.

Specific examples of the solvent include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, hydrocarbons such as toluene, xylene and hexane, and alcohols such as methanol and ethanol. The amount of these solvents used is not particularly limited, either, but the viscosity of the composition for a base material is about 10 to 10,000 poise (P) at room temperature, and the amount used is such that the viscosity is suitable for forming the base material. Is preferred.

Specific examples of the silicon compound include various silane coupling agents such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n
Alkylalkoxysilanes such as -propyltrimethoxysilane; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane and γ-glycidoxypropylmethyldiisopropenoxysilane; γ-gly Sidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, γ Alkoxysilanes having a functional group such as mercaptopropyltrimethoxysilane and γ-mercaptopropylmethyldimethoxysilane; silicone varnishes; polysiloxanes; trimethylsilanol, triethylsilane Nord, triphenyl silanol, diphenylmethyl silanol, phenyl dimethylsilanol, silanol compounds such as diphenyl silane diol; hexamethyldisilazane; such as ethyl silicate and the like.

Specific examples of the filler include, for example, silica fine powder, calcium carbonate, clay, talc, titanium oxide, zinc white, diatomaceous earth, barium sulfate, and carbon black. Among these fillers, in particular, silica fine powder, particularly, having a particle size of 7 to 50 nm (BET specific surface area of 5 to 50 nm).
Fine powder silica of about 0 to 380 m ² / g) is preferred, and among them, hydrophobic silica subjected to surface treatment is particularly preferred because of its great effect of improving strength in a preferred direction.

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

Examples of the inorganic spherical minute hollow body include a glass spherical minute hollow body, a silica balloon, a fly ash balloon, and a shirasu balloon. Specific examples of such an inorganic spherical minute hollow body include a glass spherical minute hollow body such as Karoon manufactured by Nippon Sheet Glass Co., Ltd., Scotchlite manufactured by Sumitomo 3M Co., Ltd., and Cellstar Z- manufactured by Asahi Glass Co., Ltd. 28,
Silica balloons include Q-CEL manufactured by Asahi Glass Co., Ltd., and shirasu balloons include Winlight manufactured by Ichi Kasei Co., Ltd., and Sankilite manufactured by Mitsubishi Kogyo.
Examples of the organic spherical minute hollow body include a phenol resin balloon “UCAR” manufactured by Union Carbide. These may be used alone or as a mixture of two or more. Further, those obtained by treating the surfaces of these spherical minute hollow bodies with a silane compound, polypropylene glycol or the like can also be used. These minute hollow bodies are used to reduce the weight and cost of the substrate without significantly impairing the flexibility, elongation and strength of the substrate.

When used together with the rubber-based organic polymer (a), the amount of the inorganic and organic spherical minute hollow bodies used is 3 to 50 parts, more preferably 5 to 50 parts per 100 parts of the rubber-based organic polymer (a).
~ 30 parts are preferred. If the amount is less than 3 parts, weight reduction cannot be sufficiently achieved, and if it exceeds 50 parts, the elongation and strength of the base material are undesirably reduced.

In the present invention, a base material is manufactured by crosslinking and curing a tape-shaped or sheet-shaped base material composition containing a specific rubber-based organic polymer as a main component. For example, when a curable composition containing the components (A) to (D) as a main component is used as the base material composition, the composition may be used in a solventless type or a solvent type. Since it can be used as a type that hardly uses a solvent, when using a tackifier resin or the like, these may be dissolved in a solvent in advance and then mixed with the components (A) to (D). ,
Further, the components (A) to (D) are directly mixed with a tackifying resin and the like, and the mixture is uniformly mixed by heating to a temperature near the softening point of the tackifying resin and stirring and mixing. By repeating kneading with a roll or the like, a completely solvent-free composition can be obtained. In the case of manufacturing a thick tape-to-sheet base material (hereinafter also referred to as a cured sheet), it is preferable to use a completely solventless type. As described above, a solvent may be used for the purpose of adjusting the viscosity and the like within a range in which adverse effects such as a decrease in strength due to generation of bubbles upon heating and curing do not substantially occur.

In order to produce a cured sheet from the curable composition prepared as described above, the composition is usually applied to a silicon release paper or the like, and dried and cured.

The coating method and the like are not particularly limited, and the curable composition may be applied using a usual coater. Before the application, three rolls may be passed through beforehand for the purpose of removing the bubbles entrained during mixing.

Although the viscosity of the curable composition depends on the composition, it is 10 to 10 at room temperature.
Often about 10,000P.

The thickness at the time of coating is not particularly limited, and an arbitrary thickness is possible, but the coating is performed at a normal temperature of 10 μm to 3 mm, preferably 0.1 to 1.5 mm.

After the application, the drying / curing step is started. The drying / curing conditions are from room temperature to 150 ° C. for about 0.5 to 30 minutes. When a volatile component such as a solvent is contained and foaming due to gasification is disliked, the volatile component may be vaporized from the surface with a relatively low volume that does not foam, and then cured.

The tape-shaped or sheet-shaped pressure-sensitive adhesive of the present invention is manufactured by laminating a pressure-sensitive adhesive layer on the thus obtained cured sheet as a base material.

The pressure-sensitive adhesive used in the present invention is not particularly limited. For example, a solvent-type, emulsion-type or solvent-free (oligomer-type, hot-melt-type) acrylate copolymer-based pressure-sensitive adhesive, and adhere to natural rubber and synthetic rubber. Solvent-based or hot-melt adhesive, calender-coated adhesive, silicone-based adhesive containing silicone rubber and silicone varnish, and polyether- or diene-based oligomer , A liquid curable pressure-sensitive adhesive obtained by blending the above, and other pressure-sensitive adhesives.

The pressure-sensitive adhesive as described above is applied to a substrate, dried and / or cured to produce the pressure-sensitive adhesive of the present invention.

The pressure-sensitive adhesive layer may be formed on only one side of the substrate, or may be formed on both sides. When formed on both sides, the pressure sensitive adhesive on the two sides may be the same or different.

The method for laminating the cured sheet as the base material and the pressure-sensitive adhesive layer is not particularly limited. Specific examples of the laminating method include, for example, (i) a method in which a cured sheet and a pressure-sensitive adhesive layer are separately prepared in advance and then bonded together, and (ii) a pressure-sensitive adhesive on a previously produced cured sheet. (Iii) applying a base material composition on a previously prepared pressure-sensitive adhesive layer, followed by drying and curing. However, the method is not limited to these.

The thickness of the pressure-sensitive adhesive layer thus formed is not particularly limited, but is usually about 5 μm to 1 mm, preferably about 25 μm.
100100 μm. When the pressure-sensitive adhesive layer is thick, the pressure-sensitive adhesive layer has a low cohesive force and tends to have low shear strength.

Among them, the method (ii) and the method (iii) increase the adhesion strength between the cured sheet as the base material and the pressure-sensitive adhesive layer, and perform the base-pressure-sensitive adhesion during a destructive test after bonding. It can be said that this method is preferable because it reduces the destruction at the interface of the agent layer.

The pressure-sensitive adhesive thus obtained has an elastic modulus at room temperature of 1 × 10 ⁸ dyne / cm ² or less, particularly 5 × 10 ⁷ dyne / cm ^2.
/ cm ² or less, and the preferred adhesive strength of peel adhesive strength, shear adhesive strength, and high holding power,
It can be manufactured by the same usual method as before, such as assembly of automobile products (for example, adhesion of side moldings, emblem moldings, weather strips, spoilers, etc.), electrical products, indoor furniture, display boards, building materials, etc. It can be suitably used for applications such as fixing.

〔Example〕

Hereinafter, the pressure-sensitive adhesive of the present invention will be specifically described with reference to Examples, but the present invention is not limited by these.

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 measured by an E-type viscometer 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 performed at 50 ° C. for 1 hour after the completion of the dropping, the IR spectrum was measured to be 1640 cm
^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. 7.78 g (25 mmol) were added. A solution prepared by dissolving 242 g (2.0 mol) of allyl bromide in 300 ml of toluene was added to the aqueous solution.
The solution was gradually dropped from the 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 aqueous sodium bicarbonate, it was further washed with ion-exchanged water and dried over Na ₂ SO ₄ . After removing volatile matter by evaporation, 146 g of pale yellow viscous liquid was obtained by drying under reduced pressure at 80 ° C. for 2 hours.
(95% yield). This viscous liquid was analyzed by elemental analysis, 300M
Identification of Nz ¹ HNMR, IR spectrum, etc. revealed that diallyl ether of bisphenol A Was confirmed.

IR (neat) cm ^-1 , 3070 (m, ν = _CH ), 3030 (m), 2960
(S), 2920 (S), 2860 (S) (ν _CH ), 1645 (m, ν
_{C = C} ), 1620 (S), 1520 (S), 1290 (S), 1235
(S), 1180 (S), 1025 (S), 1000 (S), 920 (S),
825 (S) Elemental analysis, calculated value C, 81.78%; H, 7.84% measured value C, 81.9%; H, 7.96% Synthesis Example 4 A stirring bar, a dropping funnel, a thermometer, a three-way cock, and a cooling pipe were provided. A 200 ml four-necked flask 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 1
l), chloroplatinic acid catalyst solvent solution (a _{H 2 PtCl 6 · 6H 2 O} 1.0g ethanol / 1,2-dimethoxyethane (1/9 V / V) to those that have been dissolved in 9 g) 40 [mu was dissolved in toluene 50ml 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. 5 at 80 ° C
At the time of reacting for an hour, when IR spectrum was taken,
The reaction was terminated at this point because the absorption derived from the olefin at 1645 cm ^-1 had completely disappeared. Dimethyl acetylenedicarboxylate (34μ, 0.24mmo) was added to the reaction mixture.
After l) was added, the toluene was distilled off under reduced pressure and then dried under reduced pressure at 80 ° C. for 1 hour to obtain 12.0 g of a pale yellow viscous liquid. 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 equipped with a stirring rod, a dropping funnel, a thermometer, a three-way cock, and a condenser was prepared. Next, under a nitrogen atmosphere, cyclic hydrogen polysiloxane (TSL-8247 manufactured by Toshiba Silicone Co., Ltd.) 25.5g (100mmo
l) and 20 ml of toluene were charged into a flask. 12.3 g of bisphenol A diallyl ether synthesized in Synthesis Example 1
(40 mmol), chloroplatinic acid catalyst solvent solution _{(H 2 PtCl 6 · 6H 2} O
1.0 g of ethanol / 1,2-dimethoxyethane (1/9 V / V) 9
g) was dissolved in 50 ml of toluene, mixed well, and then charged into a dropping funnel. At 70 ° C., the toluene solution was dropped into the flask over 1.5 hours. Another 80
At the time when the reaction was carried out at 5 ° 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 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 6 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 poly hydrogen polysiloxane 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. 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 1g ethanol 1
g, a solution dissolved in 9 g of 1,2-dimethoxyethane) (41 μl) in 50 ml of toluene was charged into a dropping funnel. The flask was placed in a 50 ° C. oil bath, and the toluene solution was dropped into the flask over 1.5 hours under a N ₂ atmosphere. When the IR spectrum was measured after the completion of the dropping, 1640 cm
^The reaction was terminated at this point because the absorption of olefin near ^-1 had completely disappeared. Dimethyl acetylenedicarboxylate (34 μ, 0.24 mmol) was added to the reaction mixture, which was then evaporated to remove volatile components, thereby obtaining 10.2 g of a slightly viscous pale yellow light liquid. The hydrosilyl group of the carbonate compound was confirmed as a strong absorption at 2170 cm ^{-1 in} the IR spectrum. Also, at 300 MHz NMR, Si- H
The intensity ratio of the proton and the peak and the Si-C H ₃ of (measured value 0.
By comparing the calculated intensity ratio with 181), it was found that the compound had a structure of the following formula on average.
If the number of Si-H groups in a unit weight is calculated based on this, it is 0.
It was 47 mol / 100 g.

Synthesis Example 7 A 14-neck 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 mmol) (LS 8600, manufactured by Shin-Etsu Chemical Co., Ltd.) was charged into the flask. Of the molecular terminal synthesized in Synthesis Example 1
Polypropylene oxide 300 g 92% is allyl group (number of moles of allyl groups 0.069 mol), toluene 230 ml, and chloroplatinic acid catalyst solvent chloride _{(H 2 PtCl 6 · 6H 2} O 1g of ethanol 1 ml,
A toluene solution consisting of 83 μl of a solution dissolved in 9 g of 1,2-dimethoxyethane) was charged into the dropping funnel. The flask was heated to 70 ° C., and the toluene solution was added dropwise at a rate of about 2 ml per minute over 5 hours. Thereafter the reaction temperature at the time of stirring up to about 6 hours 80 ° C., where the remaining allyl groups in the reaction solution was determined by IR spectroscopy, 1645 cm ^-1
It was confirmed that the carbon-carbon double bond had disappeared. Further, dimethyl acetylenedicarboxylate (118 μm, 0.83 mmol) was added to the reaction mixture, and then degassed 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 group-containing polypropylene oxide was 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 was confirmed as a strong absorption at 2150 cm ^{-1 in} the IR spectrum. Analyze 300MHz NMR spectrum,
-C H ₃ and Si-C H ₂ -combined peak intensity and Si
By comparing the intensities of the peaks 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 partially increased in molecular weight by the cyclic hydrogen polysiloxane,
It is a polypropylene oxide having a molecular terminal represented by the following formula.

Examples 1 to 20 Polymers of propylene oxide having an average molecular weight of 7960 obtained in Synthesis Example 1, Si-H group-containing organic compounds obtained in Synthesis Examples 2, 4, 5, 6 and 7, and tackifying resin ｛Straight novolak phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd., trade name: PR-50731), petroleum resin (manufactured by Mitsui Petrochemical Co., Ltd., trade name: FTR 6100), or terpene-phenol resin (manufactured by Yasuhara Yushi Co., Ltd.) , Trade name YS Polystar T-
115)｝, inorganic microspherical hollow body ｛Silans balloon (Winlight MSB 5011 manufactured by Ichi Kasei Co., Ltd.)｝, hindered phenolic antioxidant (Irganox 1010 manufactured by Ciba Geigy), and chloroplatinic acid catalyst solution (H ₂ PtCl ₆
・ 1 g of 6H ₂ O in ethanol 1 g, 1,2-dimethoxyethane 99 g
) Were weighed as shown in Table 1 and mixed well, followed by defoaming under reduced pressure. The obtained curable composition was treated with a silicon blade using a doctor blade (Siken Kako Co., Ltd.)
Co., Ltd., EK-130R), and then heated and cured at 100 ° C. for 60 minutes to obtain a cured sheet as a substrate.

On the other hand, the pressure-sensitive adhesive layer was formed as follows. That is, commercially available solvent-based acrylic pressure-sensitive adhesives
-5020) and a hardening agent (B-45, manufactured by the company) using a doctor blade, silicon release paper (EK-13, manufactured by Souken Kako Co., Ltd.)
0R) on the paste so that the glue thickness after drying is 50 μm,
It was dried and cured at 80 ° C. for 2 minutes.

The double-sided adhesive tape of the present invention was obtained by bonding the obtained pressure-sensitive adhesive layer so that air bubbles did not enter both sides of the cured sheet.

The adhesive properties of the obtained double-sided adhesive tape were measured by the following method. The results are shown in Table 1.

180mm peel strength: 2.5mm width lined with 0.1mm thick polyester film
A double-sided adhesive tape piece of cm was produced and bonded to a 1.6 mm-thick painted steel plate. After leaving this at room temperature for one day,
50% at 23 ° C and 80 ° C using Shimadzu Autograph
The 180 ° peel strength was measured at a tensile speed of mm / min. In addition, in order to examine the thermal deterioration behavior, the test piece was stored in an atmosphere at 80 ° C. for 14 days while being bonded to the coated steel sheet, and the 180 ° peel strength was measured in the same manner.

Shear adhesive strength: PVC board 2.5cm wide and 2.5cm wide, 1.6cm thick, lined with steel plate
An approximately 2.5 cm portion of the end of a painted steel sheet having a thickness of 2.5 mm was adhered with a double-sided adhesive tape. After leaving this at room temperature for one day, the tensile shear strength was measured at 23 ° C. and 80 ° C. atmosphere at a tensile speed of 50 mm / min using an autograph manufactured by Shimadzu.

Storage stability test: In order to investigate the storage stability of the pressure-sensitive adhesive, Examples 5, 6,
The double-sided pressure-sensitive adhesive prepared in 13, 14, and 20 was sandwiched between polyethylene sheets and stored at 50 ° C. for 14 days. Of these samples
The 180 ° peel strength and shear bond strength were measured as described above. The results are shown in Table 1. It is clear that no decrease in adhesive strength is observed even after storage.

Comparative Example 1 A composition comprising 100 parts of polypropylene oxide (molecular weight: 8000) having both ends blocked with a dimethoxymethylsilyl group, 20 parts of a phenol resin, 10 parts of a shirasu balloon, 10 parts of a dioctyl phosphite / amine curing catalyst, and 5 parts of methanol. An acrylic pressure-sensitive adhesive was laminated on a substrate obtained by curing the product at 120 ° C., and its adhesive strength and storage stability were tested. The results are shown in Table 1. This adhesive had poor storage stability, and when stored at 50 ° C. for 14 days, the 180 ° peel strength was reduced.

Examples 21 to 25 In order to examine the curing speed of the base material, Examples 1, 2, 5
Was cured at 100 ° C., and the change over time in the gel fraction was tracked. The results are shown in Table 2.

Comparative Example 2 A group consisting of 100 parts of polypropylene oxide (molecular weight: 8000) blocked at both ends with a dimethoxymethylsilyl group, 20 parts of a phenol resin, 10 parts of a shirasu balloon, 10 parts of a dioctyl phosphite / amine curing catalyst, and 5 parts of methanol. The material composition was cured at 120 ° C., and the change over time in the gel fraction was followed. The results are shown in Table 2.

[Operation and Effect] As described above, according to the present invention, a pressure-sensitive adhesive having flexibility and high adhesive strength is provided.

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Kazuya Yonezawa 5-12-11 Tsutsujigaoka, Tarumizu-ku, Kobe-shi, Hyogo (56) References JP-A-2-28277 (JP, A) JP-A 64-87661 (JP) , A) JP-A-57-8249 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09J 7/02 C08G 65/32

Claims (3)

(57) [Claims] 1. A pressure-sensitive adhesive obtained by laminating a pressure-sensitive adhesive layer on a substrate obtained by crosslinking and curing a curable composition containing the following components (A) to (C) as main components. (A) an organic polymer containing at least one alkenyl group in a molecule; (B) an organic compound containing at least two hydrosilyl groups in a molecule; (C) a hydrosilylation catalyst. 2. A pressure-sensitive adhesive obtained by laminating a pressure-sensitive adhesive layer on a substrate obtained by crosslinking and curing a curable composition containing the following components (A) to (D) as main components. (A) an organic polymer containing at least one alkenyl group in a molecule; (B) an organic compound containing at least two hydrosilyl groups in a molecule; (C) a hydrosilylation catalyst; and (D) storage. Stability improver. 3. The pressure-sensitive adhesive according to claim 1, wherein the curable composition contains a tackifier resin.