JPH1161066A - Pressure-sensitive adhesive laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a laminate which can be produced by extrusion with a good extrudability and has a good releasability and a suitable stickiness by forming a pressure-sensitive adhesive layer comprising a specific hydrogenated diene polymer on a smooth surface formed on at least one side of a substrate layer comprising a foam. SOLUTION: This laminate is prepd. by forming a pressure-sensitive adhesive layer comprising a hydrogenated diene polymer on a smooth surface of a substrate layer. In the diene polymer, at least 80% of double bonds at the conjugated diene parts of a polymer mainly comprising conjugated diene compd. units and having a vinyl bond content of 50-90% have been saturated. The substrate layer is a foam pref. made of polyethylene or polypropylene. The hydrogenated diene polymer is e.g. a hydrogenation product of a conjugated diene homopolymer or a random or block copolymer of a conjugated diene and an arom. vinyl compd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive laminate having an appropriate adhesive strength to a metal surface, a glass surface, a painted surface and the like, and having good releasability.

[0002]

2. Description of the Related Art At present, foams are used for cushioning materials, heat insulating materials,
It is used for various applications such as soundproofing materials and packaging materials, and is often used as various kinds of adhesive processed products such as so-called adhesive tapes and adhesive sheets for applying an adhesive to the surface. Conventionally, acrylic adhesives and rubber adhesives mainly composed of rubber such as natural rubber and polyisobutylene have been widely used as adhesives used for foamed adhesive products. These often use a solvent at the time of production, and have problems such as fire and pollution at the time of production, and also have a problem in economy due to many production steps.

[0003]

Since the present invention can be manufactured by extrusion molding, there is no problem of danger of fire or pollution at the time of manufacturing with a solvent, the number of manufacturing steps is small, and economic efficiency is high. An object of the present invention is to provide a pressure-sensitive adhesive laminate having excellent workability and good removability, and having an appropriate adhesive strength.

[0004]

That is, the present invention provides a foam (a) having a smooth layer (b) on at least one side of a base material layer (c) having a vinyl bond content of 50 to 90%. A pressure-sensitive adhesive laminate obtained by laminating a pressure-sensitive adhesive layer (e) comprising a hydrogenated diene-based polymer (d) in which a double bond of a conjugated diene portion of a polymer mainly composed of a conjugated diene compound is saturated by 80% or more. To provide.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The material of the foam (a) constituting the substrate layer (c) of the present invention is not particularly limited. For example, polyurethane foam, polyethylene foam, polypropylene foam,
Polystyrene foam, ABS foam and the like can be suitably used. Among them, polyethylene foam, polypropylene foam and polystyrene foam are preferable in terms of economy. The expansion ratio of these foams (a) is not particularly limited, but it is necessary that a smooth layer can be formed on at least one surface. The base material layer (c) of the present invention needs to have a smooth layer (b) on at least one surface of the foam (a). As a method for producing the smooth layer (b), there is a method of providing a skin layer on the foam (a) or a method of attaching another smooth film, but the latter method is applicable to a foam having a high expansion ratio. The method is preferred. The material of the smooth film is not particularly limited as long as it can be attached to the foam, but from the viewpoint of adhesion with the pressure-sensitive adhesive layer of the present invention, homo- or random-type polypropylene, Various polyethylene polymers, polystyrene polymers, PET and the like are preferable. These films may be coated with metal such as aluminum on one side, or may be bonded with metal foil such as aluminum foil. Further, a film in which two or more layers of different resins are laminated may be used. As a method of attaching a smooth film to the foam, a method using an adhesive, heat lamination,
Extrusion lamination is exemplified, but is not particularly limited as long as it does not depart from the gist of the present invention. When the pressure-sensitive adhesive layer of the present invention is laminated on a foam having no smooth layer, the adhesive strength between the foam / pressure-sensitive adhesive layer is weak, and when the pressure-sensitive adhesive laminate is peeled off from the adherend, the pressure between the foam / pressure-sensitive adhesive layer is low. Although the pressure-sensitive adhesive layer may remain on the adherend due to peeling, the adhesion between the foam and the pressure-sensitive adhesive layer is improved by forming a smooth layer, and the pressure-sensitive adhesive layer remains on the adherend. Can be prevented.

The (d) hydrogenated diene polymer used in the pressure-sensitive adhesive layer of the present invention includes, for example, a homopolymer of a conjugated diene, a random copolymer of a conjugated diene and an aromatic vinyl compound, and a copolymer of an aromatic vinyl compound. A block copolymer comprising a polymer block and a polymer block of a conjugated diene compound; a block copolymer comprising a polymer block of an aromatic vinyl compound and a random copolymer block of a conjugated diene / aromatic vinyl compound; and a conjugated diene compound A block copolymer consisting of a polymer block of a conjugated diene / aromatic vinyl compound and a taper shape in which an aromatic vinyl compound consisting of a polymer block of a conjugated diene compound, an aromatic vinyl compound and a conjugated diene gradually increases Block copolymer consisting of blocks, random copolymer of conjugated diene / aromatic vinyl compound A block copolymer comprising a lock, an aromatic vinyl compound and a conjugated diene, and a tapered block in which the aromatic vinyl compound is gradually increased; a polybutadiene block having 1,2- and 3,4-vinyl bonds of 30% by weight or less and a conjugated diene Examples include hydrogenated products of a diene-based polymer (hereinafter, also referred to as “pre-hydrogenated polymer”) such as a block polymer composed of a polymer block of a compound. Further, the hydrogenated diene polymer of the present invention may be modified with a functional group, and at least one kind selected from an acid anhydride group, a carboxyl group, a hydroxyl group, an amino group, an isocyanate group, and an epoxy group. A modified functional group having a functional group can also be used. The ratio of the conjugated diene compound / aromatic vinyl compound constituting the pre-hydrogenated polymer is not particularly limited in the present invention, but is preferably 1
00/0 to 40/60 (weight ratio, the same applies hereinafter), more preferably 93/7 to 60/40, and most preferably 93/7.
７０70/30.

The conjugated diene compound used for the hydrogenated diene polymer component includes 1,3-butadiene,
Isoprene, 2,3-dimethyl-1,3-butadiene,
1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,
Examples thereof include 3-octadiene, 3-butyl-1,3-octadiene, and chloroprene. In order to obtain a hydrogenated diene polymer which is industrially usable and has excellent physical properties,
1,3-butadiene, isoprene and 1,3-pentadiene are preferred, and 1,3-butadiene and isoprene are particularly preferred. As the aromatic vinyl compound, styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene, divinylbenzene, N, N-dimethyl-
p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene, vinylpyridine and the like,
Styrene and α-methylstyrene are preferred.

The pre-hydrogenated polymer may be a polymer in which a polymer molecular chain is extended or branched via a coupling residue by using a coupling agent. As the coupling agent used at this time, for example, diethyl adipate, divinylbenzene, methyldichlorosilane, silicon tetrachloride, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, dimethylchlorosilicon, tetrachlorogermanium, 1,2- Dibromoethane, 1,4-chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized linseed oil, tolylene diisocyanate,
1,2,4-benzene triisocyanate and the like can be mentioned.

As the (d) hydrogenated diene polymer used in the present invention, a hydrogenated product of a blend of two or more pre-hydrogenated polymers is also preferably used.
Further, a blend of two or more hydrogenated diene polymers is also suitable as the hydrogenated diene polymer used in the present invention.

The (c) hydrogenated diene polymer used in the present invention is obtained by hydrogenating a polymer mainly composed of a conjugated diene compound. In the polymer, it is necessary that the double bond of the conjugated diene portion is preferably 80% or more, more preferably 90% or more, and if it is less than 80%, the weather resistance is poor and it is not preferable. The preferred number average molecular weight of the (d) hydrogenated diene polymer used in the present invention is from 1 to 70.
10,000, more preferably 50,000 to 600,000, and if less than 10,000,
It is not preferable because the cohesive force of the pressure-sensitive adhesive layer is reduced to cause adhesive residue. On the other hand, if it exceeds 700,000, the appearance of the molded product becomes poor, which is not preferable. In the (d) hydrogenated diene-based polymer used in the present invention, the proportion of vinyl bonds in the conjugated diene portion is 50 to 90% by weight, preferably 60 to 90% by weight, and more preferably 65 to 85% by weight. is there. If the ratio of vinyl bonds in the conjugated diene portion is less than 50%, the adhesive strength may be insufficient, which is not preferable. The (d) hydrogenated diene polymer used in the present invention is described in, for example,
No. 75512, page 4, upper right column, line 13 to page 6, lower left, line 1 can be obtained.

In the pressure-sensitive adhesive layer comprising the hydrogenated diene polymer of the present invention (d), a phosphate ester compound, a tackifying resin,
Known additives such as an olefin resin, a rubbery polymer, an antistatic agent, an antioxidant, a lubricant, an antifogging agent, a coloring agent, an ultraviolet absorber, and an ultraviolet stabilizer can also be blended. For example, as the phosphate compound, a phosphate ester and a derivative thereof can be suitably used. Examples of the phosphate compound include a phosphate ester, a phosphate ester salt, an alkyl phosphate ester, an alkyl phosphate ester salt, an alkyl ether phosphate ester, an alkyl ether phosphate ester salt, an alkyl phenol phosphate ester, an alkyl phenol phosphate ester, and an alkyl phenol. Examples include ether-type phosphates, alkylphenol ether-type phosphates, higher alcohol phosphates, higher alcohol phosphates, and the like. As the phosphate compound, an alkyl phosphate ester, an alkyl phosphate ester salt, an alkyl ether phosphate ester, and an alkyl ether phosphate ester salt are preferable. For example, alkyl-type phosphates include lauryl phosphate, alkyl-type phosphates include octyl phosphate potassium, lauryl phosphate potassium, stearyl phosphate potassium, lauryl phosphate sodium, and alkyl ether-type phosphates include lauryl. Examples of ether phosphates, stearyl ether phosphates, alkyl ether type phosphates include lauryl ether phosphate potassium, stearyl ether phosphate potassium, and the like.
It is not limited to these. Further, examples of the phosphoric ester compound include a monoester type, a diester type, and a triester type, and they can be used alone or in combination of two or more. The amount of the phosphate compound to be added is 10 parts by weight or less, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the hydrogenated diene polymer (d). If the amount is less than 0.1 part by weight, the adhesive strength after long-term sticking will increase remarkably, and the peelability may decrease.
When the amount exceeds 10 parts by weight, so-called glue residue which causes fogging on the adherend at the time of peeling is not preferable.

As the tackifier, (d) those which are compatible with the hydrogenated diene-based polymer and improve the adhesive strength are preferable. For example, aliphatic hydrocarbon resins, terpene resins, cumarone / indene resins, aromatic hydrocarbons Resins, rosin resins, phenolic resins and the like are preferably used. As the olefin-based resin, those which are compatible with the (d) hydrogenated diene-based polymer are preferable, and for example, polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1 and the like are suitably used. Examples of the rubbery polymer include EBM (ethylene-butene copolymer), EVA, EPM, EPD
M, an ethylene-based copolymer obtained by a metallocene-based polymerization catalyst, and the like are preferably used. As the stabilizer, antioxidants such as hindered fenur type and phosphite type, ultraviolet absorbers such as benzotriazole type, benzophenone type and salicylate type, and light stabilizers such as hindered amine type are preferably used. . Also, if necessary, talc, silica, inorganic fillers such as charcoal,
An organic filler such as carbon fiber or amide fiber may be contained.

The pressure-sensitive adhesive laminate of the present invention is produced, for example, as follows. (A) A method in which an adhesive layer (e) extruded using an extruder on a base material layer is thermally bonded. (B) For example, the adhesive layer (e) is applied to the smooth surface of the base material layer by the method (a). ) Can be manufactured by lamination by a known method such as extrusion lamination. Further, although it is not preferable in terms of using a solvent, the adhesive laminate of the present invention can also be produced by a method of dissolving the components constituting the adhesive layer in an organic solvent, followed by coating and drying. The thickness of the pressure-sensitive adhesive layer of the present invention is appropriately selected depending on the desired properties and applications of the pressure-sensitive adhesive laminate.
m or more.

[0014]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but it should not be construed that the invention is limited thereto without departing from the spirit of the present invention. Various evaluations in Examples and Comparative Examples were performed as follows. The amount (% by weight) of the vinyl aromatic compound bonded was measured by infrared absorption at 679 cm @ -1 absorption of a phenyl group. The vinyl bond content (%) of the conjugated diene portion was calculated by the Hampton method using infrared analysis. Hydrogenation rate (%) Using ethylene tetrachloride as a solvent, 1
Calculated by 1 H-NMR spectrum. Gel permeation chromatography (GPC) at 135 ° C. using trichlorobenzene as a number average molecular weight solvent for the hydrogenated diene copolymer
Was calculated in terms of polystyrene. Adhesive strength The initial adhesive strength was measured using the prepared adhesive laminate according to JIS Z-
According to the 0237 method, the test was performed under the conditions of an adherend SUS304 steel plate, a peel angle of 180 °, and a peel speed of 300 mm / min. Adhesion between base material and pressure-sensitive adhesive layer Easiness of peeling of the pressure-sensitive adhesive layer from the prepared pressure-sensitive adhesive laminate was determined according to the following criteria. When the adhesive layer is to be peeled from the substrate, the adhesive layer is broken and it is extremely difficult to peel off.

The components used in the formulations of the examples and comparative examples are as follows. 1. Component (C) (C-1) A polyethylene foam sheet having one side adhered to the aluminum side of a PET film obtained by evaporating aluminum (150 μm thick). (C-2) PE film on one side of the polyethylene foam sheet (150 μm thickness) (C-3) A polypropylene foam sheet with a PP film attached to one surface (150 μm thickness) (C-4) Polyethylene foam sheet (150 μm thickness) 2 , (A) hydrogenated diene copolymer shown in component table 1 (a-1) ~ ( A-
3) was synthesized. As (A-4), a hydrogenated styrene-butadiene-styrene block copolymer (SEBS) (trade name: Clayton G1652) manufactured by Shell Co., Ltd. was used. Table 1 summarizes the microstructure, number average molecular weight, and hydrogenation rate of these hydrogenated diene copolymers.

[0016]

[Table 1] * 1) BD: butadiene * 2) IP: isoprene * 3) ST: styrene * 4) A part: polymer part mainly composed of aromatic vinyl compound * 5) A: A part, B: random Copolymer part

Examples 1 to 5 A 15 μm-thick pressure-sensitive adhesive layer (b) having the composition shown in Table 2 was extrusion-molded with a T die on the base material layer composed of the component (c-1). Using an extruder, extrusion temperature 240 ° C,
Extrusion lamination was performed at a cooling roll temperature of 20 ° C. to obtain an adhesive laminate having a total thickness of 165 μm. The obtained pressure-sensitive adhesive sheet was evaluated. As a result, the obtained pressure-sensitive adhesive laminate had good adhesion, adhesion between the substrate and the pressure-sensitive adhesive layer, and good moldability. Table 2 shows the evaluation results.

COMPARATIVE EXAMPLE 1 A total of 165 .mu.m in thickness of the 150 .mu.m-thick base material layer composed of the component (c-1) and the 15 .mu.m-thick pressure-sensitive adhesive layer (b) having the composition shown in Table 2 was used. Pressure-sensitive adhesive films were prepared under the same conditions as in Examples 1 to 3, and evaluated. As a result, since the pressure-sensitive adhesive composition of the pressure-sensitive adhesive laminate of Comparative Example 1 was out of the range of the present invention, good pressure-sensitive adhesive strength could not be obtained. Table 2 shows the evaluation results. Comparative Example 2 A pressure-sensitive adhesive having a total thickness of 165 μm of a 150 μm-thick base material layer composed of the component (c-4) and a 15 μm-thick pressure-sensitive adhesive layer (b) composed of the composition shown in Table 2 Films were prepared under the same conditions as in Examples 1 to 3 and evaluated. As a result, the pressure-sensitive adhesive laminate of Comparative Example 2 was inferior in adhesion between the substrate and the pressure-sensitive adhesive layer because the configuration of the substrate was out of the range of the present invention. Table 2 shows the evaluation results.

[0019]

[Table 2]

[0020]

The pressure-sensitive adhesive laminate of the present invention can be produced by extrusion molding, has excellent moldability, has an appropriate pressure, and has excellent adhesion between the substrate layer and the pressure-sensitive adhesive layer. Adhesive laminates with good properties are obtained, and surface protection films, adhesive tapes, adhesive labels, adhesives used to prevent scratches on steel plates, painted steel plates, decorative steel plates, glass plates, resin plates, decorative plywood, etc. It can be used for sheet, building material sheet, assembly, furniture protection sheet, etc. and has great industrial value.

Claims (1)

[Claims] 1. A polymer mainly composed of a conjugated diene compound having a vinyl bond content of 50 to 90% on a smooth surface of a base material layer (c) having a smooth layer (b) on at least one surface of a foam (a). A pressure-sensitive adhesive layer obtained by laminating a pressure-sensitive adhesive layer (e) comprising a hydrogenated diene-based polymer (d) in which the double bond of the conjugated diene portion is saturated by 80% or more.