JP5544990B2 - Adhesive laminate - Google Patents

Description

  The present invention relates to an adhesive laminate.

  The adhesive laminated body which has a base material and an adhesive body layer is used with the form of an adhesive sheet or an adhesive tape, for example. The adhesive laminate is required to be adhered to the adherend with a desired force during use, and is required to have a removability that can be peeled off from the adherend so that there is no adhesive deposit. . The adhesive residue means that when the substrate is peeled from the state in which the substrate, the adhesive layer and the adherend are in close contact in this order, part or all of the adhesive layer is integrated with the substrate. It means that it remains on the adherend without being peeled off.

  In Patent Document 1, a polyether polymer (A) having one or more alkenyl groups in one molecule and a compound containing an average of two or more hydrosilyl groups (Si—H groups) in one molecule ( A composition containing B) and a hydrosilylation catalyst is applied on release paper and then cured to form an adhesive layer, and a polyester film is laminated as a support on the adhesive layer. A sheet is described. In order to obtain good skin fixability, the peel adhesive strength of the pressure-sensitive adhesive layer is as high as 3.5 to 5.2 N / 25 mm, for example. In Comparative Example 1, it is indicated that the skin fixability is poor when the peel adhesive strength is 0.4 N / 25 mm.

JP 2008-132206 A

In recent years, when manufacturing electrical parts, electronic materials, and the like, protective sheets and protective tapes are frequently used. The main purpose is to protect these parts and materials from scratches and dust when stored or transported. Since such a protective sheet and a protective tape are peeled and removed at the time when the temporary fixing and protection of components are finished, it is preferable that the pressure-sensitive adhesive layer has a low peel adhesive force and can be easily peeled off.
However, the lower the peel adhesive strength of the pressure-sensitive adhesive layer, the smaller the adhesive force between the base material and the pressure-sensitive adhesive layer. Therefore, when the protective sheet or the protective tape is peeled and removed, adhesive residue is likely to occur.

Moreover, as a support for the pressure-sensitive adhesive layer, a polyester base material is suitable because it is relatively inexpensive and has a good balance between performance and cost, in addition to excellent performance such as mechanical strength, chemical resistance, and insulation. It is.
However, it is difficult for the polyester base material to obtain a good adhesive force with the pressure-sensitive adhesive layer, and if the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer is not high, the pressure-sensitive adhesive layer and the base material are easily peeled off, resulting in adhesive residue. For this reason, it is difficult to realize a pressure-sensitive adhesive laminate having a low pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer using a polyester-based substrate.

  The present invention has been made in view of the above circumstances, and the base material is made of a polyester-based material, and the adhesive strength between the base material and the pressure-sensitive adhesive layer is good even though the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer is low. It aims at providing a certain adhesion layered product.

The present invention is the following [1] to [4].
[1] A pressure-sensitive adhesive laminate having a polyester-based substrate and an adhesive layer provided in close contact with the polyester-based substrate, the surface of the polyester-based substrate being in close contact with the adhesive layer, A cured surface treated with a rubber primer composition, wherein the pressure-sensitive adhesive layer contains the following polyoxyalkylene polymer (A), the following curing agent (B), and a hydrosilylation catalyst (C). obtained by curing the composition, peel adhesion is Ri der less 1N / 25 mm, the rubber-based primer composition, a synthetic rubber containing chlorine, polyisocyanate compound, and a compound containing a hydrolyzable silyl group adhesive laminate, characterized in der Rukoto rubber-based primer composition comprising.
(A) A polyoxyalkylene polymer having an alkenyl group, an average number of alkenyl groups per molecule of 1.8 or more, and a number average molecular weight of 1,000 to 50,000.
(B) A curing agent comprising a polyorganosiloxane represented by the following formula (1).

(In the formula, m is an integer of 0 to 100, n is an integer of 2 to 100, R ¹ , R ² , R ³ , R ⁷ , R ⁸ , R ⁹ are each independently a hydrogen atom or a carbon number of 1 to And R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a monovalent group represented by the following formula (2).)
-(OR ') _t- ZR "(2)
Wherein R ′ is an alkylene group having 1 to 20 carbon atoms, Z is a divalent linking group, R ″ is a hydrocarbon group or hydrogen atom having 1 to 20 carbon atoms, and t is an integer of 1 to 200. is there.)

[2] The hydrosilyl group / alkenyl group molar equivalent ratio is 0, which represents the ratio of the total number of hydrosilyl groups of the curing agent (B) to the total number of alkenyl groups of the polyoxyalkylene polymer (A). The adhesive laminate according to [1], which is less than .9.
[3] The pressure-sensitive adhesive laminate according to [1] or [2], wherein the hydrosilylation catalyst (C) includes a platinum-based catalyst.
[4] The pressure-sensitive adhesive laminate according to [1] to [3], wherein a part or all of the alkylene groups constituting the polyoxyalkylene polymer (A) are propylene groups.

  According to the present invention, since the base material is made of a polyester-based material and the adhesive strength between the base material and the pressure-sensitive adhesive layer is good even though the peel strength of the pressure-sensitive adhesive layer is low, It is possible to obtain a pressure-sensitive adhesive laminate that hardly peels off from the material and hardly generates adhesive residue on the adherend.

The number average molecular weight (Mn), mass average molecular weight (Mw), and molecular weight distribution (Mw / Mn) in this specification are determined by gel permeation chromatography using a calibration curve prepared using a standard polystyrene sample with a known molecular weight. It is a polystyrene conversion molecular weight obtained by measuring.
The average hydroxyl value (unit: mgKOH / g) in the present specification is a measured value based on JIS-K-1557-6.4.
In this specification, the molecular weight converted from the hydroxyl value of the polymer is referred to as a hydroxyl-converted molecular weight MW (OH). The relationship between the hydroxyl value and the hydroxyl equivalent molecular weight MW (OH) is represented by the following formula.
Hydroxyl equivalent molecular weight MW (OH) = number of hydroxyl groups per molecule of compound used as initiator × 56,100 / hydroxyl value

In the present specification, the adhesion property is a property of adhering to an adherend with light pressure and optionally re-peeling. A pressure-sensitive adhesive is a substance that has adhesiveness and adheres to an adherend with light pressure. It has removability and is used for temporary adhesion. On the other hand, the adhesive is different from the pressure-sensitive adhesive in that it has a permanent adhesive performance.
In the present specification, the adhesiveness may be classified according to the peeling adhesive strength (peeling strength from the adherend). Slight adhesion when peel adhesion exceeds 0 N / 25 mm and less than 1 N / 25 mm, low adhesion when peel adhesion exceeds 1 N / 25 mm and less than 8 N / 25 mm, peel adhesion exceeds 8 N / 25 mm and 15 N / 25 mm The following cases are referred to as medium adhesion, and the case where the peel adhesive strength exceeds 15 N / 25 mm and is 50 N / 25 mm or less is called strong adhesion. Unless otherwise specified, the peel adhesive strength conforms to the 180-degree peeling method specified in JIS-Z-0237 (1999) -8.3.1 and follows the following test method.
That is, in a 23 ° C. environment, a 1.5 mm thick bright annealed stainless steel plate (SUS304 (JIS)) was attached to a pressure sensitive adhesive sheet test piece (width: 25 mm), and a rubber roll having a mass of 2 kg. Crimp. After 30 minutes, the peel strength (180 degree peel, tensile speed 300 mm / min) is measured using a tensile tester specified in JIS-B-7721. The value of the peel strength after 30 minutes of sticking obtained in this way is defined as “peel adhesive strength” in the present invention.

  The pressure-sensitive adhesive laminate of the present invention may have any form, but a pressure-sensitive adhesive sheet or pressure-sensitive adhesive tape is preferable. The adhesion body (adherence substrate) is a molded body having adhesiveness. A pressure sensitive adhesive sheet is a sheet having adhesiveness. However, in this specification, the thickness and the sheet are not distinguished from each other. An adhesive sheet is a laminated body which has a sheet-like base material and an adhesive body layer as a component. Moreover, an adhesive tape (pressure sensitive adhesive tape) is a tape-shaped adhesive sheet, and means the form which has sufficient length with respect to a width | variety.

<Polyester base material>
The pressure-sensitive adhesive laminate of the present invention has a polyester base material (sometimes simply referred to as a base material) and a pressure-sensitive adhesive layer provided in close contact with the polyester base material.
The polyester base material in the present invention is a base material made of a polyester material. The base material functions to mechanically support the pressure-sensitive adhesive layer.
Examples of the polyester material include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polybutylene naphthalate (PBN). These resins may have other copolymer components and may be a mixture with other resins. In addition, the polyester material may contain various additives. Examples of the additive include an antistatic agent, a UV absorber, and a stabilizer.

The form of the substrate is not particularly limited. For example, a film, a woven fabric, a nonwoven fabric, etc. are mentioned. In particular, a film is preferable in that the workability of the pressure-sensitive adhesive laminate is excellent. In the case of a woven fabric or a non-woven fabric, it may consist only of a polyester material or a composite with other materials.
The thickness of the polyester base material is not particularly limited, and is appropriately selected according to the purpose of use. The thickness suitable as a support for the pressure-sensitive adhesive layer is 5 to 300 μm, and more preferably 10 to 150 μm.

<Primer treatment>
In the present invention, the surface of the polyester-based substrate that is in close contact with the pressure-sensitive adhesive layer is a treated surface treated with the rubber-based primer composition. By performing the treatment using the rubber-based primer composition, the adhesive force between the base material and the pressure-sensitive adhesive layer is improved, and the base material and the pressure-sensitive adhesive layer are hardly separated. Adhesive residue on the adherend is less likely to occur.
The rubber-based primer composition used in the present invention is a composition containing a rubber component (natural rubber and / or synthetic rubber), a polyisocyanate compound, and a compound containing a hydrolyzable silyl group.

The rubber component of the rubber-based primer composition in the present invention is preferably a synthetic rubber classified into JIS K6397 (however, the description of polyethylene shall be read as polyolefin), and among these, a synthetic rubber containing chlorine ( a) is more preferred.
The rubber primer composition comprises a synthetic rubber (a) containing chlorine, a polyisocyanate compound (b), a silane coupling agent (c1) having a ketimine group, an oxazolidine group or an amino group, and a polyalkyl silicate (c2). One containing at least one compound (c) having a hydrolyzable silyl group selected from the group and a solvent (d) is preferred.

[Synthetic rubber containing chlorine (a)]
The chlorine content in the synthetic rubber (a) containing chlorine is 5 to 70% by mass. When the chlorine content is 5% by mass or more, the effect of improving the adhesion between the substrate and the pressure-sensitive adhesive layer can be sufficiently obtained. On the other hand, when the chlorine content exceeds 70% by mass, the viscosity of the composition becomes too high, and workability deteriorates. The chlorine content is preferably 10 to 70% by mass, and particularly preferably 40 to 70% by mass.
The synthetic rubber (a) containing chlorine is not particularly limited as long as the chlorine content is a synthetic rubber in the above range. Polychloroprene, chlorinated products of isoprene-based synthetic rubber, chlorinated polyethylene, chlorinated polypropylene, chlorinated polyethylene / propylene Examples include copolymers, chlorinated polybutadiene, chlorinated polystyrene, chlorinated polybutadiene / styrene copolymers, chlorosulfonated polyethylene, chlorosulfonated polyethylene / vinyl acetate copolymers, and the like. These may be used alone or in combination of two or more.
Although the number average molecular weight of the synthetic rubber (a) containing chlorine is not particularly limited, it is preferably about 10,000 to 1,000,000, and particularly has a suitable strength and stability if it is about 20,000 to 500,000. It is preferable from the viewpoint of the stability of the adhesive improvement effect.

[Polyisocyanate compound (b)]
As the polyisocyanate compound (b), polyisocyanates such as tolylene diisocyanate, phenylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, triphenylmethane triisocyanate, Alternatively, addition products of these polyisocyanates, for example, adducts using trimethylolpropane or glycol, these isocyanurate-modified products, carbodiimide-modified products, allophanate-modified products, burette-modified products and the like can be mentioned. These may be used alone or in combination of two or more.
Among the examples listed above, isocyanurate-bonded TDI, isocyanurate-bonded HDI, isocyanurate-bonded TPDI and the like having an isocyanurate ring are preferable because of their high polarity and excellent adhesion improvement effect.
In particular, polyfunctional isocyanurate compounds having an isocyanurate ring are suitable, and specific examples include Death Module IL and Death Module HL (both trade names) manufactured by Sumitomo Bayer Urethane Co., Ltd.

As for the usage-amount of a polyisocyanate compound (b), 5-100 mass parts is preferable with respect to 100 mass parts of a rubber component. When the polyisocyanate compound (b) is 5 parts by mass or more, the effect of improving the adhesion between the base material and the pressure-sensitive adhesive layer can be sufficiently obtained. On the other hand, if the polyisocyanate compound (b) exceeds 100 parts by mass, the storage stability tends to deteriorate.
The amount of the polyisocyanate compound (b) used is more preferably 5 to 80 parts by mass, and further preferably 5 to 30 parts by mass.
Further, as the polyisocyanate compound (b), a compound obtained by reacting polyisocyanate with aminosilane or mercaptosilane may be used.

[Compound (c) having hydrolyzable silyl group]
The compound (c) having a hydrolyzable silyl group is selected from the group consisting of a silane coupling agent (c1) having a ketimine group, an oxazolidine group or an amino group, and a polyalkyl silicate (c2). These may be used alone or in combination of two or more.
The silane coupling agent (c1) is a silane coupling agent represented by the following formula (3), in which the organic functional group (—R ¹¹ ) is a ketimine group, an oxazolidine group, or an amino group.
R ¹¹ SiX ₃ (3)
In the formula (3), R ¹¹ is an organic functional group having a substituent bonded to the organic material. X is a hydrolyzable group that reacts with an inorganic material, preferably a chlorine atom or an alkoxy group. -SiX ₃ is a hydrolyzable silyl group. In the hydrolyzable silyl group, three X bonded to Si may be the same as or different from each other.
The silane coupling agent (c1) is a silane coupling agent represented by the above formula (3), and the organic functional group (—R ¹¹ ) is not a ketimine group, an oxazolidine group, or an amino group. By reacting an unsubstituted silane coupling agent (c ′) with a ketimine compound, an oxazolidine compound or an amine compound, an organic functional group (—R ¹¹ ) of the unsubstituted silane coupling agent (c ′) is obtained. , Ketimine group, oxazolidine group or amino group. Alternatively, the silane coupling agent (c1) can be obtained from a commercial product.

Examples of the unsubstituted silane coupling agent (c ′) include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, and γ-aminopropyltrimethoxy. Silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ-chloropropyltrimethoxy Examples include silane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, and trimethylchlorosilane. . These may be used alone or in combination of two or more.
Among these, those in which the organic functional group is an amino group can be used as they are as the silane coupling agent (c1).

The polyalkyl silicate (c2) is a compound represented by the following formula (4). (R ¹² O) ₃ Si— is a hydrolyzable silyl group.
(R ¹² O) ₃ Si [—O—Si (OR ¹³ ) ₂ ] _s OR ¹⁴ (4)
(In formula, R < ¹² >, R <^13> , R < ¹⁴ > is a C1-C6 alkyl group mutually independently, and s is an integer of 2-6.)
Specific examples of the polyalkyl silicate (c2) include polymethyl silicate, polyethyl silicate, polypropyl silicate, polybutyl silicate, polypentyl silicate, polyhexyl silicate and the like. These may be used alone or in combination of two or more.
Of these, polymethyl silicate, polyethyl silicate, and polypropyl silicate are preferable, and polymethyl silicate is particularly preferable in terms of availability and high reactivity.

  As for the usage-amount of the compound (c) which has a hydrolysable silyl group, 5-100 mass parts is preferable with respect to 100 mass parts of a rubber component. When the compound (c) having a hydrolyzable silyl group is 5 parts by mass or more, the adhesion to the polyester base material is good, and when it exceeds 100 parts by mass, the coated material becomes brittle and easily peels off. The amount of the compound (c) having a hydrolyzable silyl group is more preferably 5 to 80 parts by mass, and further preferably 5 to 30 parts by mass.

[Solvent (d)]
The solvent (d) of a primer composition should just be inert with respect to an isocyanate group, and can use well-known various solvents suitably. Specific examples include aromatic hydrocarbons such as benzene, xylene and toluene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate and butyl acetate; diethyl ether, tetrahydrofuran and dioxane. And ethers. Two or more of these may be mixed and used. Of these, ethyl acetate or toluene is preferred because of its low boiling point and quick drying.
As for content of the solvent (d) in a primer composition, 10-8000 mass parts is preferable with respect to 100 mass parts of a rubber component. When the amount is less than 10 parts by mass, the viscosity of the primer composition becomes too high and the applicability is deteriorated. If it exceeds 8000 parts by mass, a sufficient primer film thickness may not be obtained, and the effect of improving adhesiveness may not be sufficiently obtained. The content is more preferably 100 to 5000 parts by mass, and particularly preferably 500 to 4000 parts by mass.

[catalyst]
You may make the primer composition contain the catalyst of isocyanurate reaction as needed. As such a catalyst, tertiary amine compounds; or metal catalysts such as metal soap compounds, metal alkylates and metal chelates are preferably used.
Examples of the tertiary amine compound include N, N, N ′, N′-tetramethylpropylenediamine, N, N-dimethylbenzylamine, triethylenediamine, pentamethylenediethylenetriamine, morpholine-based amine, triethylamine and the like. Among these, N, N, N ′, N′-tetramethylpropylenediamine and N, N-dimethylbenzylamine are preferable from the viewpoint of storage stability. Specifically, Kao's Kaorizer No. 2, Kaorizer No. 20 is mentioned.
As the metal soap compound, a carboxylate such as tin, zinc, bismuth, zirconium, cobalt, calcium, or cerium can be used.
Examples of the metal alkylate include titanium and zirconium alkoxides such as tetrapropoxy titanium and tetrabutoxy titanium, and condensates thereof.
As the metal chelate, chelates of titanium, aluminum, zirconium, iron, cobalt and the like, for example, aluminum acetylacetonate can be used.
When the primer composition contains a catalyst, the content is preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the rubber component. If it is less than 0.01 part by weight, the effect of adding the catalyst cannot be sufficiently obtained. If the amount exceeds 100 parts by mass, the primer composition may gel and storage stability may be reduced. The content of the catalyst is preferably 0.05 to 50 parts by mass, and more preferably 0.1 to 30 parts by mass.

In addition to the above-described components, the primer composition appropriately contains components such as a rust inhibitor, a filler, a thickener, an antioxidant, an inorganic pigment, an organic pigment, an ultraviolet absorber, a water absorbent, and a thixotropic agent. You may mix | blend.
Examples of the rust preventive agent include various rust preventive pigments, zinc phosphate, tannic acid derivatives, phosphate esters, basic sulfonates, and the like. Examples of the plasticizer include phthalic acid esters, adipic acid esters, sebacic acid esters, tricresyl phosphate, and the like. Examples of the filler include calcium carbonate, carbon black, glass powder, clay, powdered silica gel, ultrafine powdered silicic acid, molecular sieves and the like.
In addition, it is preferable not to use a plasticizer for a primer composition, and it is preferable not to contain ester type plasticizers, such as a dioctyl phthalate especially. This is because when an ester plasticizer is used, the adhesive force between the cured product (pressure-sensitive adhesive layer) and the substrate is reduced, and adhesive residue tends to occur.

  The method for producing the primer composition is not particularly limited. For example, a rubber component, a polyisocyanate compound (b), a hydrolyzable silyl group-containing compound (c), a solvent (d), and other additives that are optionally blended are charged into a reaction vessel, such as a ball mill. It can be produced by a method of sufficiently kneading using a mixing apparatus and uniformly dispersing the components.

<Curable composition>
The pressure-sensitive adhesive layer in the present invention is formed by coating a curable composition on the treated surface of a polyester-based substrate and curing the curable composition.
The curable composition concerning this invention contains a polyoxyalkylene polymer (A), a hardening | curing agent (B), and a hydrosilylation catalyst (C).
<Polyoxyalkylene polymer (A)>
The polyoxyalkylene polymer (A) has an alkenyl group. The alkenyl group in the present invention means a monovalent group containing one carbon-carbon double bond active for reaction with a hydrosilyl group (Si—H group). The alkenyl group is preferably an aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms, preferably 2 to 6 carbon atoms.
Examples of the aliphatic unsaturated hydrocarbon group include a vinyl group, an allyl group, a methylvinyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group. The terminal carbon atom preferably has a double bond.

As the alkenyl group, a monovalent group represented by the following formula (5) or (6) is particularly preferable in that the synthesis reaction of the polyoxyalkylene polymer (A) is easy. In the following formulae, R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrogen atom or a methyl group.
H ₂ C═C (R ¹⁵ ) − (5)
HC (R ¹⁶ ) = CH− (6)

The average number of alkenyl groups per molecule of the polyoxyalkylene polymer (A) is 1.8 or more. When the average number is 1.8 or more, sufficient curability in the pressure-sensitive adhesive layer is easily obtained. The upper limit of this average number is 6.0 or less from the point of the softness | flexibility of an adhesive body layer, and the range of 2.0-3.0 is preferable.
In the present invention, when the polyoxyalkylene polymer (A) is a mixture of two or more polyoxyalkylene polymers having different numbers of alkenyl groups, the average number of alkenyl groups per molecule is Is the average number of alkenyl groups.

Examples of the alkylene group constituting the polyoxyalkylene polymer (A) include an ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, propylene group, butylene group, and methyltrimethylene group. These alkylene groups are obtained by ring-opening polymerization of the corresponding cyclic ether compound or epoxide compound.
Examples of cyclic ether compounds include tetrahydrofuran and oxetane. Examples of the epoxide compound include ethylene oxide, propylene oxide, butylene oxide, and the like.
The alkylene group constituting the polyoxyalkylene polymer (A) is preferably a propylene group particularly from the viewpoint of flexibility and transparency of the pressure-sensitive adhesive layer, and a part of the alkylene group constituting the polyoxyalkylene polymer (A) or It is preferable that all are propylene groups. Specifically, 50% by mass or more of the alkylene groups constituting the polyoxyalkylene polymer (A) is preferably a propylene group, more preferably 80% by mass or more, and most preferably 100% by mass.

The polyoxyalkylene polymer (A) is preferably obtained by converting the terminal hydroxyl group of the polyoxyalkylene polyol (A ′) into an alkenyl group or a monovalent group containing an alkenyl group.
As the polyoxyalkylene polyol (A ′), polyoxytetramethylene polyol, polyoxyethylene polyol, polyoxypropylene polyol, and polyoxyethylene polyoxypropylene polyol are preferable, and polyoxypropylene polyol is more preferable.

The polyoxyalkylene polyol (A ′) is obtained by subjecting the cyclic ether compound or epoxide compound to ring-opening addition polymerization to an initiator in the presence of a polymerization catalyst.
The average number of terminal hydroxyl groups per molecule of the polyoxyalkylene polyol (A ′) is the active hydrogen of the initiator used for producing the polyoxyalkylene polyol (A ′) (the above cyclic ether compound or epoxide compound). Is equal to the number of hydroxyl groups or amino group hydrogen atoms) that can react. The initiator is preferably a compound having 2 to 6 active hydrogens in one molecule.

As the initiator used for the production of the polyoxyalkylene polyol (A ′), hydroxyl group-containing compounds such as polyhydric alcohols and polyhydric phenols are preferable. An initiator may be used individually by 1 type and may use 2 or more types together.
Examples of the compound having 2 active hydrogens include dihydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, and dipropylene glycol. Examples of the compound having 3 active hydrogens include trihydric alcohols such as glycerin and trimethylolpropane. Further, it is preferable to use a high hydroxyl group polyoxyalkylene polyol obtained by subjecting these compounds to ring-opening addition polymerization of alkylene oxide, preferably propylene oxide. The number of hydroxyl groups in the high hydroxyl group polyoxyalkylene polyol is preferably 2 or 3, and the hydroxyl equivalent molecular weight MW (OH) is preferably from 3,000 to 30,000.

  Polymerization catalysts used for the production of polyoxyalkylene polyol (A ′) include alkali metal compound catalysts (sodium-based catalysts, potassium-based catalysts, cesium-based catalysts, etc.), cationic polymerization catalysts, double metal cyanide complex catalysts, phosphazenium compounds. Etc. An alkali metal compound catalyst is preferable from the viewpoint of availability of the catalyst, and a double metal cyanide complex catalyst is preferable from the viewpoint of obtaining a low by-product polyol.

The number average molecular weight of the polyoxyalkylene polymer (A) is 1,000 to 50,000. Hardened | cured material (adhesive body layer) obtained as it is 50,000 or less tends to become slightly adhesive. If it is less than 1,000, the cured product (adhesive layer) tends to be brittle. The number average molecular weight is more preferably 2,000 to 50,000, and particularly preferably 2,000 to 30,000.
In this invention, when a polyoxyalkylene polymer (A) is a mixture, the number average molecular weight of a polyoxyalkylene polymer (A) is a value of the number average molecular weight in the whole mixture.

The polyoxyalkylene polymer (A) can be produced by first synthesizing a polyoxyalkylene polyol (A ′) and converting the terminal hydroxyl group into an alkenyl group or a monovalent group containing an alkenyl group.
For example, it is possible to use a method in which the hydroxyl group of polyoxyalkylene polyol (A ′) is alcoholated to -OM (M is an alkali metal) and then reacted with a halogenated hydrocarbon having an alkenyl group such as allyl chloride. This method is preferable because it is general and the raw materials are easily available and the reaction yield is high.
Alternatively, a method in which a compound having a functional group capable of reacting with a hydroxyl group and an alkenyl group is reacted with the hydroxyl group of the polyoxyalkylene polyol (A ′) to introduce an alkenyl group via an ester bond, a urethane bond, a carbonate bond, or the like. Can be used.

<Curing agent (B)>
The curing agent (B) is a polyorganosiloxane represented by the above formula (1). That is, the curing agent (B) has n hydrosilyl groups (Si—H groups) (n is 2 or more). The hydrosilyl group of the curing agent (B) reacts with the alkenyl group of the polyoxyalkylene polymer (A) in the presence of the hydrosilylation catalyst (C) to form a crosslinked structure. A hardening | curing agent (B) may be used individually by 1 type, and may use 2 or more types together.
In Formula (1), R ^{1 to} R ³ and R ^{7 to} R ⁹ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group include an alkyl group and a phenyl group. From the viewpoint of versatility, an alkyl group having 1 to 20 carbon atoms is preferable, and a methyl group is more preferable.
R ^{4 to} R ⁶ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a monovalent group represented by the above formula (2).
In Formula (2), R ′ is an alkylene group having 1 to 20 carbon atoms, preferably an ethylene group or a propylene group. When a plurality of R ′ are present in one molecule, they may be the same as or different from each other.
Z is a divalent linking group. For example, -O-, -NH-, an ester bond, a urethane bond, etc. are mentioned.
R ″ is a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Examples of the hydrocarbon group include an alkyl group and a phenyl group. From the viewpoint of versatility, an alkyl group having 1 to 20 carbon atoms is preferable. A methyl group is more preferable.
t is an integer of 1 to 200, preferably 1 to 50, more preferably 1 to 20 in terms of good adhesion.
R ^{1 to} R ⁹ may be different from each other, but are preferably the same as each other.
Moreover, in Formula (1), n is 2-100, 2-50 are preferable at the point which raises cohesion force, and 5-50 are more preferable. m is 0-100, 0-50 are preferable at the point which improves a softness | flexibility, and 0-10 are more preferable.

  The content of the curing agent (B) in the curable composition is such that the hydrosilyl group of the curing agent (B) is based on the total number of alkenyl groups of the polyoxyalkylene polymer (A) present in the curable composition. The hydrosilyl group / alkenyl group molar equivalent ratio, which represents the ratio of the total number of moles, is preferably less than 0.9, more preferably 0.5 or less. When the molar equivalent ratio is less than 0.9, the resulting cured product (adhesive layer) tends to be slightly tacky. The lower limit of the molar equivalent ratio is preferably 0.2 or more, more preferably 0.3 or more, from the viewpoint that sufficient curability is easily obtained.

<Storage stabilizer for curing agent (B)>
The curable composition can contain a storage stabilizer for the curing agent (B) as required.
Examples of the storage stabilizer for the curing agent (B) include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, and an organic peroxide.
The curable composition containing the curing agent (B) converts the hydrosilyl group (Si—H group) of the curing agent (B) into a Si—OH group when left for a long time or when moisture is mixed. Reaction can occur. By suppressing the reaction by adding the above storage stabilizer, it is possible to suppress the thickening of the curable composition and lengthen the pot life. The storage stabilizer content is a storage stabilizer / hydrosilyl group molar ratio, which represents the ratio of the number of moles of storage stabilizer to the total number of moles of hydrosilyl groups in the curing agent (B) present in the curable composition. Is preferably 10 ⁻⁶ to 10 ⁻¹ .

<Hydrosilylation catalyst (C)>
The hydrosilylation catalyst (C) may be any catalyst that promotes the reaction (hydrosilylation reaction) between the alkenyl group of the polyoxyalkylene polymer (A) and the hydrosilyl group of the curing agent (B). It can be used as appropriate.
As specific examples, catalysts such as platinum-based catalysts, rhodium-based catalysts, cobalt-based catalysts, palladium-based catalysts, and nickel-based catalysts can be used.
Of these, platinum-based catalysts are preferred in terms of reactivity. The platinum-based catalyst refers to a compound containing platinum among the catalysts that promote the hydrosilylation reaction. For example, a chloroplatinic acid, a platinum-vinylsiloxane complex, and a platinum-olefin complex are mentioned. Examples of the platinum-vinylsiloxane complex include platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, platinum-1,3,5,7-tetravinyl-1,3, Examples include 5,7-tetramethylcyclotetrasiloxane complex. Examples of platinum-olefin complexes include Ptx (ViMe ₂ SiOSiMe ₂ Vi) y, Pt [(MeViSiO) ₄ ] z (where x, y, z represent a positive integer, Me represents a methyl group, Vi Is a vinyl group.).
Among these, from the viewpoint of the activity of the catalyst, a platinum complex catalyst not containing a conjugate base of a strong acid as a ligand is preferable, a platinum-vinylsiloxane complex is more preferable, and platinum-1,3-divinyl-1,1, A 3,3, -tetramethyldisiloxane complex or a platinum-1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane complex is particularly preferred.

The content of the hydrosilylation catalyst (C) in the curable composition is not particularly limited, but the hydrosilylation catalyst is based on the total number of alkenyl groups of the polyoxyalkylene polymer (A) present in the curable composition. The molar ratio of hydrosilylation catalyst / alkenyl group, which represents the molar ratio of (C), is preferably 10 ⁻⁸ to 10 ⁻¹ , more preferably 10 ⁻⁶ to 10 ⁻³ . If it is in the said range, a suitable hardening rate and stable sclerosis | hardenability will be easy to be obtained.

<Additives>
In addition to the above components, the curable composition may appropriately contain additives as necessary.
As the additive, known components can be appropriately used in the pressure-sensitive adhesive. Examples include fillers, reinforcing materials, stabilizers, flame retardants, antistatic agents, mold release agents, and antifungal agents.
In addition, it is preferable not to use a plasticizer, and it is particularly preferable not to include an ester plasticizer such as dioctyl phthalate. This is because when an ester plasticizer is used, the adhesive force between the cured product (pressure-sensitive adhesive layer) and the substrate is reduced, and adhesive residue tends to occur.

Examples of the filler or reinforcing material include carbon black, aluminum hydroxide, calcium carbonate, titanium oxide, silica, glass, bone powder, wood powder, or fiber flake.
Examples of the stabilizer include an antioxidant, an ultraviolet absorber, and a light stabilizer. These can be known ones.
Examples of the flame retardant include chloroalkyl phosphate, dimethylmethylphosphonate, ammonium polyphosphate, or organic bromine compound.
Examples of the antistatic agent include ionic compounds and conductive compounds. Examples of the release agent include wax, soaps, and silicone oil.
Examples of the antifungal agent include pentachlorophenol, pentachlorophenol laurate, or bis (tri-n-butyltin) oxide.

<Solvent>
The curable composition of the present invention has a low viscosity and can be applied without a solvent, but may contain a solvent.
The solvent is not particularly limited. For example, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, ethers, ester alcohols, ketone alcohols, ether alcohols , Ketone ethers, ketone esters or ester ethers.
Among these, aromatic hydrocarbons, ketones, and esters are preferable because of their good solubility.
When adding a solvent to a curable composition, it is preferable that the addition amount is 500 mass parts or less with respect to 100 mass parts of a polyoxyalkylene polymer (A), and is 1-100 mass parts. Is more preferable. When the addition amount exceeds 500 parts by mass, the cured product may shrink as the solvent volatilizes.

<Method for producing adhesive laminate>
In order to produce the pressure-sensitive adhesive laminate of the present invention, the surface of the polyester base material on which the pressure-sensitive adhesive layer is laminated is treated in advance with the rubber-based primer composition. Specifically, a rubber primer composition is applied on one surface of a polyester base material and dried. Known methods can be used as appropriate for the coating method and drying method of the rubber-based primer composition.
The thickness of the primer layer after drying is preferably from 0.01 to 10 μm, more preferably from 0.02 to 5 μm, from the viewpoint of the adhesive strength between the substrate and the pressure-sensitive adhesive layer.

Next, the curable composition is applied on the treated surface of the polyester-based substrate treated with the rubber-based primer composition.
The coating method of a curable composition is not specifically limited, A well-known method can be used suitably. For example, a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray coater or the like can be used.
When the pressure-sensitive adhesive laminate is a long product, for example, the curable composition may be applied onto the primer-treated surface of the substrate drawn out from the roll and heated and dried in an in-line oven.

Subsequently, the curable composition coated on the substrate is heated and cured to form an adhesive layer.
The heating conditions at the time of curing are preferably in the range of 1 to 60 minutes at 40 to 180 ° C. After the heating, it is preferable to further cure at room temperature to completely cure the curable composition.
The thickness of the pressure-sensitive adhesive layer is preferably in a range where good adhesiveness can be obtained and the balance with the thickness of the substrate is good. For example, 3-100 micrometers is preferable and 10-60 micrometers is more preferable.
Thus, an adhesive laminate in which the adhesive layer is provided in close contact with the substrate is obtained.

  As another method, after applying a curable composition on a separator (release paper), this is heated and cured to form an adhesive layer, and a treated surface of a polyester base material is laminated thereon. The pressure-sensitive adhesive laminate of the present invention can also be produced by a method of bonding them together.

  The pressure-sensitive adhesive laminate of the present invention may have various functional layers as necessary in addition to the base material and the pressure-sensitive adhesive layer. Examples of the functional layer include a conductive layer and an antireflection layer.

<Adhesive laminate>
The pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive laminate of the present invention comprises a cured product obtained by curing the curable composition, and has a peel adhesive strength of 1 N / 25 mm or less. The lower limit value of the peel adhesive strength is preferably 1 g / 25 mm (0.001 N / 25 mm) or more in terms of obtaining good adhesion to an adherend. A more preferable peel adhesive strength is 0.05 to 0.5 N / 25 mm or less.
The peel adhesive strength of the pressure-sensitive adhesive layer can be controlled by the composition of the curable composition. For example, when the number average molecular weight of the polyoxyalkylene polymer (A) is decreased, the peel adhesive strength tends to decrease. Further, when the molar equivalent ratio of hydrosilyl group / alkenyl group is decreased, the peel adhesive strength tends to decrease.

The pressure-sensitive adhesive laminate of the present invention can be easily peeled off from the adherend because the pressure-sensitive adhesive layer has a peel adhesive strength of 1 N / 25 mm or less and is slightly adhesive.
Moreover, as shown in the below-mentioned Example, the adhesiveness of a base material and an adhesive body layer improves favorably by using especially a rubber-type primer composition as a composition which carries out the primer process of the polyester-type base material. The reason is not clear, but it is considered that good wettability of the curable composition constituting the pressure-sensitive adhesive layer according to the present invention can be obtained on the treated surface treated with the rubber-based primer composition. . When the wettability is good, the adhesive property between the pressure-sensitive adhesive layer and the base material is improved by spreading the curable composition over the entire surface. Furthermore, since the rubber-based primer composition contains a polyisocyanate compound and a compound containing a hydrolyzable silyl group, it is considered that the pressure-sensitive adhesive layer and the substrate are more firmly bonded by these actions.
Therefore, the adhesive laminate of the present invention provides good adhesion between the substrate and the adhesive layer while the adhesive layer is slightly adhesive. Therefore, the removability is good, and the occurrence of adhesive residue is prevented when peeling from the adherend.

Moreover, as the adhesive laminated body of this invention is shown by the below-mentioned comparative example, the surface which is not processed with the rubber-type primer composition of a polyester-type base material has weak adhesiveness with an adhesive body layer. Therefore, this surface can be used in place of a separator (release paper) without performing a release agent treatment. For example, when the pressure-sensitive adhesive laminate is a long object, it can be wound without using a separator. Further, since no release agent treatment is required, contamination with the silicone release agent is not generated. Therefore, it is suitable for application to electronic equipment such as semiconductor elements and liquid crystal substrates.
Moreover, since a highly transparent polyester resin can be used as a base material, it can also be applied to uses requiring transparency.

<Use of adhesive laminate>
The application of the pressure-sensitive adhesive laminate of the present invention is not particularly limited. For example, protective sheets for electronic materials such as electronic substrates and IC chips; protective sheets for optical members such as polarizing plates, light diffusing plates, light diffusing sheets, prism sheets; protective sheets for various displays; protective sheets for automobiles; Surface protective film; decorative sheet for wall covering; surface protection of products such as metal plate, coated steel plate, synthetic resin plate, decorative plywood, heat reflecting glass, and the like.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.
Each component used in Examples and Comparative Examples is as follows.
[Polyoxyalkylene polymer (A)]
Polyoxyalkylene polymer (A1): A polyoxypropylene polymer obtained in the following Production Example 1 and having an average of 2.0 allyl groups per molecule and having a number average molecular weight of 10,000.
[Curing agent (B)]
Curing agent (B1): A compound in which R ^{1 to} R ⁹ in the formula (1) are all methyl groups, m is 0, and n is 40. (Manufactured by Shin-Etsu Chemical Co., Ltd., hydrogen-modified silicone composition, product name: KF-99, number of functional groups: 40 g / mol, kinematic viscosity at 25 ° C .: 20 mm ² / s).
[Hydrosilylation catalyst (C)]
Hydrosilylation catalyst (C1): Platinum vinyldisiloxane complex (manufactured by Toray Dow Corning, platinum catalyst, product name: SRX212)

[Reference Production Example 1: Production of double metal cyanide complex catalyst]
Zinc hexacyanocobaltate (hereinafter referred to as TBA-DMC catalyst) having tert-butyl alcohol as an organic ligand was produced by the following method. The polyol X in this example is a polyol having a number average molecular weight (Mn) of 1000 obtained by addition polymerization of propylene oxide to dipropylene glycol.
First, an aqueous solution consisting of 10.2 g of zinc chloride and 10 g of water was placed in a 500 ml flask, and while maintaining the aqueous solution at 40 ° C., stirring at 300 rpm (300 rpm), 4.2 g An aqueous solution composed of potassium hexacyanocobaltate (K ₃ [Co (CN)] ₆ ) and 75 g of water was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was further stirred for 30 minutes. Thereafter, a mixture of 40 g of ethylene glycol mono-tert-butyl ether (hereinafter abbreviated as EGMTBE), 40 g of tert-butyl alcohol (hereinafter abbreviated as TBA), 80 g of water, and 0.6 g of polyol X was obtained. It added in the said mixture and stirred at 40 degreeC for 30 minutes, and also at 60 degreeC for 60 minutes. The obtained reaction mixture was filtered for 50 minutes under pressure (0.25 MPa) using a circular filter plate having a diameter of 125 mm and a quantitative filter paper for fine particles (No. 5C manufactured by ADVANTEC Co.) to obtain a solid. separated.
Next, a mixture comprising 18 g of EGMTBE, 18 g of TBA, and 84 g of water was added to the cake containing the double metal cyanide complex and stirred for 30 minutes, followed by pressure filtration (filtration time: 15 minutes). It was. To the cake containing the double metal cyanide complex obtained by filtration, a mixture of 54 g EGMTBE, 54 g TBA, and 12 g water was added and stirred for 30 minutes, and the double metal cyanide having an organic ligand was stirred. A slurry of EGMTBE / TBA containing the complex was obtained. This slurry was used as a TBA-DMC catalyst.
About 5 g of this slurry was weighed into a flask, dried roughly with a nitrogen stream, and then dried under reduced pressure at 80 ° C. for 4 hours. As a result of weighing the obtained solid, it was found that the concentration of the double metal cyanide complex contained in the slurry was 4.70% by mass.

[Production Example 1: Production of polyoxyalkylene polymer (A1)]
800 g of polyoxypropylene diol (hydroxyl equivalent molecular weight MW (OH) = 1000) as an initiator and the TBA-DMC catalyst obtained in Reference Production Example 1 were charged into a 10 L stainless steel pressure-resistant reactor equipped with a stirrer. The amount of TBA-DMC catalyst used was 50 ppm with respect to the finished mass.
After the atmosphere in the reactor was replaced with nitrogen, the temperature was raised to 140 ° C., and 80 g of propylene oxide (hereinafter referred to as PO) was charged into the reactor and allowed to react with stirring. This is a process for initially supplying a small amount of PO to activate the TBA-DMC catalyst.
Next, after the pressure in the reactor has dropped, 7120 g of PO is supplied with stirring, and the reactor is stirred for 11 hours while maintaining the temperature in the reactor at 140 ° C. and the stirring speed at 500 rpm (500 rpm). The polymerization reaction was allowed to proceed. A polyol (a1) was thus obtained. The average hydroxyl value of the polyol (a1) was 11.8 mgKOH / g, and the number average molecular weight (Mn) was 10,000.
To the obtained polyol (a1), a methanol solution of 1.05 equivalents of sodium methoxide of the hydroxyl group was added, and methanol was distilled off under reduced pressure by heating to convert the terminal hydroxyl group of the polyol (a1) into sodium alkoxide. did. Next, after allyl chloride was reacted with this, unreacted allyl chloride was removed, and the by-produced salt was purified and removed to perform allylation. Thus, a polyoxypropylene polymer (A1) in which the hydroxyl groups at both ends were substituted with allyl groups was obtained.

[Reference Production Example 2: Preparation of rubber-based primer composition]
A rubber-based primer composition P obtained by mixing a rubber component, a polyisocyanate compound (b), a compound (c) having a hydrolyzable silyl group, and a solvent (d) in the composition shown in Table 1 (unit: parts by mass). −1 to P-5 were prepared. Each component shown in Table 1 is as follows.
Rubber component (1): Super Clone 814 (product name, manufactured by Nippon Paper Chemicals Co., Ltd., chlorinated polypropylene, chlorine content: 41% by mass)
Ester polymer: Polyester TP-220 (product name, manufactured by Nippon Synthetic Chemical Co., Ltd., molecular weight: 16000, glass transition temperature: 70 ° C.)
Polyisocyanate compound (1): Desmodur HL (product name, manufactured by Bayer, compound name: polyisocyanate)
Polyisocyanate compound (2): Coronate L (product name, manufactured by Nippon Polyurethane Co., Ltd., compound name: TDI adduct)
Silane coupling agent (1): γ-aminopropyltrimethoxysilane silane coupling agent (2): vinyltrimethoxysilane silane coupling agent (3): γ-glycidoxypropyltrimethoxysilane solvent (1)

[Examples 1 to 4 and Comparative Example 2]
(Curable composition)
A polyoxyalkylene polymer (A), a curing agent (B), and a hydrosilylation catalyst (C) were mixed in the formulation (unit: part by mass) shown in Table 2 to obtain a curable composition. The table shows the ratio of the total number of moles of hydrosilyl groups of the curing agent (B) to the total number of moles of alkenyl groups of the polyoxyalkylene polymer (A) present in the curable composition. The value of the molar ratio of hydrosilylation catalyst / alkenyl group, which represents the molar equivalent ratio of groups and the ratio of the number of moles of hydrosilylation catalyst (C) to the total number of moles of alkenyl groups of polyoxyalkylene polymer (A), Show.

(Primer treatment of substrate)
A PET film (A4 size: 29.7 cm × 21 cm, manufactured by Toyobo Co., Ltd., polyester film, product name: E5001, thickness 25 μm) having a thickness of 25 μm and not surface-treated was prepared as a polyester base material.
One side of the PET film was subjected to primer treatment using the primer compositions shown in Table 2. That is, the primer composition was applied using an applicator and then dried at 110 ° C. for 1 minute. The thickness of the primer layer after drying was 1 μm.

(Manufacture of adhesive laminate)
A curable composition having the composition shown in Table 2 was coated on the surface (treated surface) subjected to primer treatment of the PET film using an applicator.
The film thickness of the curable composition immediately after coating was about 15 μm. This was heated at 110 ° C. for 2 minutes to be cured and dried, and further cured at 23 ° C. and humidity of 50% for 7 days. Thus, an adhesive laminate in which an adhesive layer made of a cured product of the curable composition was laminated on the substrate was obtained. The cured adhesive layer had a thickness of 15 μm and a peel adhesive strength of 0.6 N / 25 mm.

[Comparative Example 1]
In Example 1, an adhesive laminate was obtained in the same manner as in Example 1 except that the base material was changed to the PET film that was not subjected to primer treatment.

(Coating appearance test)
About the adhesion laminated body obtained in each case, the coating external appearance test was done. The results are shown in Table 2. The test was carried out visually. The case where the coating film (adhesive layer) was uniformly obtained was rated as “◯”, and the case where the coating film was not uniformly obtained or the coating film was repelled was marked as “X”.

(Evaluation of adhesion between substrate and adhesive layer: finger rub test)
About the adhesion laminated body obtained by each case, the finger-rub test was done by the following method, and the adhesiveness of an adhesion body layer and a base material was evaluated. The results are shown in Table 2. The length direction of the base material is the X direction, the width direction is the Y direction, and the thickness direction is the Z direction.
First, the end of the obtained pressure-sensitive adhesive laminate is cut with a cutter at a cutting plane (YZ plane) perpendicular to the X direction, and then on a plane so that the pressure-sensitive adhesive layer is on the upper side. Fix it. An index finger is placed on the cutting position of the cutter, and the index finger is moved 10 times back and forth along the X direction to rub the adhesive layer near the cutting position. The width for moving the index finger back and forth is 3 cm in the front and back with the cutting position as the center. The case where the pressure-sensitive adhesive layer is not peeled even after rubbing 10 times is evaluated as “◯” (passed), and the case where peeling occurs less than 10 times is defined as “x” (failed). In the case of failure, the number of times of rubbing until peeling occurred is shown in the table.

As shown in the results of Table 2, in the pressure-sensitive adhesive laminates of Examples 1 to 4 in which a primer treatment was performed on a polyester base material using a rubber-based primer composition, the pressure-sensitive adhesive layer was slightly tacky, Good adhesion between the pressure-sensitive adhesive layer and the polyester base material was obtained. In contrast, in Comparative Example 1 where the primer treatment was not performed on the base material and in Comparative Example 2 where the primer treatment was performed using the polyester primer composition, the adhesion between the pressure-sensitive adhesive layer and the base material was poor. It was enough.
Moreover, in the comparative example 2, the external appearance of the adhesion body layer was not uniform, and the surface became a skin shape. This indicates that, on the treated surface treated with the polyester-based primer composition, good wettability was not obtained when the composition was applied, and the coating film was repelled.

Claims (4)

A pressure-sensitive adhesive laminate comprising a polyester-based substrate and an adhesive layer provided in close contact with the polyester-based substrate, wherein the surface of the polyester-based substrate that is in close contact with the adhesive layer is a rubber primer. A treated surface treated with the composition;
The pressure-sensitive adhesive layer is obtained by curing a curable composition containing the following polyoxyalkylene polymer (A), the following curing agent (B), and the hydrosilylation catalyst (C), and has a peel adhesion of 1 N / 25 mm. Ri der below,
The rubber-based primer composition, a synthetic rubber containing chlorine, polyisocyanate compounds, and hydrolysis-sensitive adhesive laminate of a rubber-based primer composition der wherein Rukoto containing silyl group-containing compound.
(A) A polyoxyalkylene polymer having an alkenyl group, an average number of alkenyl groups per molecule of 1.8 or more, and a number average molecular weight of 1,000 to 50,000.
(B) A curing agent comprising a polyorganosiloxane represented by the following formula (1).

(In the formula, m is 0 to 100, n is an integer of 2 to 100, R ¹ , R ² , R ³ , R ⁷ , R ⁸ , R ^9.
Are independently of each other hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. R ⁴ , R ⁵ , and R ⁶ are each independently hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a monovalent group represented by the following formula (2). )
-(OR ') tZR "(2)
Wherein R ′ is an alkylene group having 1 to 20 carbon atoms, Z is a divalent linking group, R ″ is a hydrocarbon group or hydrogen atom having 1 to 20 carbon atoms, and t is an integer of 1 to 200. is there.)   The molar ratio of hydrosilyl group / alkenyl group is less than 0.9, which represents the ratio of the total number of moles of hydrosilyl groups in the curing agent (B) to the total number of moles of alkenyl groups in the polyoxyalkylene polymer (A). The pressure-sensitive adhesive laminate according to claim 1, wherein   The pressure-sensitive adhesive laminate according to claim 1 or 2, wherein the hydrosilylation catalyst (C) contains a platinum-based catalyst.   The adhesion laminated body as described in any one of Claims 1-3 whose one part or all part of the alkylene group which comprises the said polyoxyalkylene polymer (A) is a propylene group.