JPH1060387A - Pressure-sensitive self-adhesive laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pressure-sensitive self-adhesive film or sheet which can be produced by extrusion and has excellent moldability, suitable self-adhesive power, and good releasability and weatherability. SOLUTION: A pressure-sensitive self-adhesive laminate is prepd. by forming, on at least one side of a substrate layer, a self-adhesive layer contg. 100 pts.wt. hydrogeneated diene polymer obtd. by hydrogenating conjugated diene-derived double bonds of a polymer mainly comprising a random copolymer of a conjugated diene and an arom. vinyl compd. and 0.01-10 pts.wt. phosphoric ester compd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a base material layer and a pressure-sensitive adhesive layer having good adhesion to a metal surface, a glass surface, a painted surface and the like on one surface of the base material layer and good releasability. Pressure-sensitive adhesive laminates, especially films and sheets.

[0002]

2. Description of the Related Art Conventionally, acrylic adhesives and rubber adhesives mainly composed of rubbers such as natural rubber and polyisobutylene have been widely used as adhesives for pressure-sensitive adhesive films. Since many use solvent systems,
During manufacturing, there were problems such as fire danger, pollution, and economics due to the large number of manufacturing processes.

In recent years, in order to solve such a problem, a method has been used in which a base layer and an adhesive layer are produced by co-extrusion using a hot-melt adhesive. As a pressure-sensitive adhesive film produced by coextrusion molding, for example, there is a surface protective film. The surface protective film is used to prevent scratches and stains on the surface of a coated steel plate, a metal plate, a synthetic resin plate, a glass plate, a decorative steel plate and the like during processing and transportation. The surface protection film has a structure in which an adhesive layer is formed on one surface of a base material layer made of thermoplastic resin or paper, and has a suitable adhesiveness and adheres to the surface of various adherends after use. So-called releasability, which can be easily peeled off without being contaminated with an agent, must be good. As this kind of surface protective film, for example, a film using ethylene as a main component, for example, EVA as an adhesive layer on one surface of a base layer made of a polyolefin resin is known, but a tackifier resin is not used in combination. And sufficient tackiness cannot be obtained. In addition, when used outdoors, sufficient peelability cannot be obtained due to an increase in adhesive strength. On the other hand, to the pressure-sensitive adhesive layer, a general formula ABA (where A is a styrene polymer block, B is a butadiene polymer block, an isoprene polymer block, or a butadiene polymer or an isoprene polymer is hydrogenated by 80% or more. Shows copolymer block)
The use of a block copolymer represented by the formula (1) is known, but if a tackifier resin is not used in combination, the molding processability is poor and the intended product cannot be obtained. In addition, when used outdoors, sufficient peelability cannot be obtained due to an increase in adhesive strength.

[0004]

Since the present invention can be manufactured by extrusion molding, there is no danger of fire or pollution at the time of manufacturing with a solvent, the number of manufacturing steps is small, and economy is good. Excellent moldability, moderate adhesive strength,
Another object of the present invention is to provide a pressure-sensitive adhesive laminate having good releasability and good weather resistance, particularly a film and a sheet. Hereinafter, the film and the sheet will be described.

[0005]

That is, the present invention relates to a base material layer (a) and at least one surface of the base material layer having the following (b)
An object of the present invention is to provide a pressure-sensitive adhesive laminate having an adhesive layer (d) containing 0.01 to 10 parts by weight of the following (C) with respect to 0 parts by weight. (B) a hydrogenated diene polymer in which the double bond of the conjugated diene portion of the polymer mainly composed of a random copolymerized portion of a conjugated diene compound and an aromatic vinyl compound is saturated (c) a phosphate ester compound

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. As the base material layer (a) of the present invention,
Known materials such as a styrene-based thermoplastic resin, paper, foam, and the like can be used. An example of the thermoplastic resin is an olefin-based resin. The olefin-based resin is a resin obtained by polymerizing one or more monoolefins by a high-pressure method or a low-pressure method, and is preferably polyethylene, polypropylene, or polybutene.
1, poly 4-methylpentene-1. The polyolefin resin may be a homopolymer or a copolymer obtained by copolymerizing another monomer as shown below. As preferred copolymerization components of the olefin resin,
For example, ethylene (excluding when the main polymer is polyethylene), propylene (excluding when the main polymer is polypropylene), butene-1 (excluding when the main polymer is polybutene-1), pentene-1 , Hexene-1, heptene-1, octene-1, etc.
-Olefin, 4-methylpentene-1 (excluding the case where the main polymer is 4-methylpentene-1), 2-methylpropene-1, 3-methylpentene-1, 5-methylhexene-1, 4-methyl Branched α-olefins such as hexene-1,4,4-dimethylpentene-1, monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid and crotonic acid, maleic acid, fumaric acid, itaconic acid and citraconic acid; Acrylic acid or methacrylic acid ester such as dicarboxylic acid or monoester thereof, methyl methacrylate, methyl acrylate, ethyl acrylate, vinyl acetate, vinyl ester of saturated carboxylic acid such as vinyl propionate, styrene, α-styrene, p
-Aromatic vinyl compounds such as methylstyrene, acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, and aconitic anhydride; α, β-unsaturated nitriles such as acrylonitrile and methacrylonitrile; Diene monomers such as hexadiene, dicyclopentadiene, and ethylidene norbornene, as well as acrylamide, methacrylamide, and maleimide are used. These copolymerizable monomers may be used alone or in combination of two or more. The form of the copolymer when these are copolymerized is not particularly limited, and may be, for example, any of a random type, a block type, a graft type, and a mixed type thereof. The amount of these copolymer components is preferably 30% by weight or less, more preferably 20% by weight.
It is as follows.

These olefin resins may be used alone or in combination of two or more. Further, these olefin-based resins may be a single layer or
It may be composed of more than two layers. Further, to these olefinic resins, talc, silica, silica balloon, if necessary, within a range that does not substantially impair the features of the present invention.
Known anti-blocking agents such as glass balloons and polymer microspheres, organic antibacterial agents, inorganic antibacterial agents, antistatic agents, antioxidants, lubricants, antifogging agents, coloring agents, ultraviolet absorbers, ultraviolet stabilizers, etc. May be added. As the paper, there is no particular limitation on the material of the paper, and for example, various papers described in “All Paper Guide-Dictionary of Paper” edited by Paper Industry Times Co., Ltd. can be suitably used. These papers may be used alone or in combination of two or more. In addition, these papers may be those in which a resin such as polyethylene or polypropylene is coated on one or both sides of the paper. There is no particular limitation on the material of the foam as the foam, and foams such as polyethylene, polypropylene, and polystyrene can be suitably used.

The (ii) hydrogenated diene copolymer of the present invention comprises:
Polymers mainly composed of a random copolymerized portion of a conjugated diene compound and an aromatic vinyl compound (hereinafter referred to as “pre-hydrogenated polymer”
) Is hydrogenated. The proportion of the random copolymerized portion in the polymer before hydrogenation is preferably at least 50% by weight, more preferably at least 60% by weight, further preferably at least 70% by weight. When the proportion of the random copolymerized portion is less than 50% by weight, the resulting weather-resistant pressure-sensitive adhesive films and sheets tend to have insufficient tackiness. Further, in the random copolymer part, 1, 2, and 3, 4 relative to all conjugated dienes in the random copolymer part
The ratio of the bound conjugated diene is preferably 60% by weight or more, more preferably 65% by weight or more, and further preferably 70% by weight or more. The proportion of this conjugated diene is 60%
If it is less than 3, the obtained weather-resistant, pressure-sensitive adhesive film or sheet tends to have insufficient tackiness.

The (ii) hydrogenated diene copolymer used in the present invention comprises a conjugated diene compound and an aromatic vinyl compound. The conjugated diene compound used here includes 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene,
-Methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene, etc., and can be used industrially. In order to obtain a hydrogenated diene polymer having excellent physical properties, 1,3-butadiene, isoprene and 1,3-pentadiene are preferred, 1,3-butadiene and isoprene are particularly preferred, and the aromatic vinyl compound is , Styrene, α-methylstyrene, p-
Methylstyrene, t-butylstyrene, divinylbenzene, N, N-dimethyl-p-aminoethylstyrene,
N, N-diethyl-p-aminoethylstyrene, vinylpyridine and the like can be mentioned, and styrene and α-methylstyrene are preferable.

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 95/5 to 5/5.
40/60, more preferably 93/7 to 50/50
(Weight ratio). The pre-hydrogenated polymer is mainly composed of a random copolymer of a conjugated diene compound and an aromatic vinyl compound.In some cases, the polymer molecular chain contains other polymer blocks as described below. May be. As the polymer block, for example, an aromatic vinyl compound polymer, a polybutadiene polymer mainly containing 1,4-bonds,
And a tapered polymer comprising an aromatic vinyl compound and a conjugated diene and gradually increasing the aromatic vinyl compound. The presence of these polymer blocks slightly impairs the physical properties of the component (b), but improves the handleability by reducing the blocking properties of the material, and may be industrially useful. The proportion of the polymer block in the total molecular chain of the polymer before hydrogenation is not particularly limited, but is preferably 50% by weight or less, and is preferably 40% by weight or less.
% Or less, more preferably 30% by weight or less. When the proportion of the polymer block exceeds 50% by weight, the obtained weather-resistant pressure-sensitive adhesive films and sheets tend to have reduced adhesiveness. The pre-hydrogenated polymer may have a structure extended or branched via a coupling agent residue. As the coupling agent used in this case, 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.

The hydrogenated diene copolymer (b) used in the present invention is obtained by hydrogenating a double bond of a conjugated diene moiety in a polymer before hydrogenation. In this hydrogenation, the pre-hydrogenated polymer can be used alone or in combination of two or more. The hydrogenation rate of the hydrogenated diene copolymer is preferably 80%, more preferably 8%.
5% or more, more preferably 90% or more. 80%
When it is less than 1, adhesiveness is excellent, but heat resistance and weather resistance are inferior, adhesive strength after long-term application is remarkably increased, and adhesive residue tends to be easily generated on an adherend during peeling. The hydrogenated diene polymer has a polystyrene-equivalent number average molecular weight (hereinafter, referred to as “number average molecular weight”) of preferably 50,000 to 700,000, and more preferably 50,000 to 600,000. If the molecular weight is less than 50,000, the cohesive force of the obtained pressure-sensitive adhesive film and sheet having good weather resistance and the cohesive strength of the sheet tends to decrease, and adhesive tends to remain on the adherend during peeling. If it exceeds 700,000, workability, adhesiveness, and the like tend to be insufficient. The hydrogenated diene copolymer as described above can be produced, for example, by the method disclosed in JP-A-3-72512.

Further, the hydrogenated diene copolymer used as the component (b) may be a modified product obtained by introducing one or more functional groups into the hydrogenated diene copolymer. Examples of the functional group include a carboxyl group, an acid anhydride group, a hydroxyl group, an epoxy group, an amino group, an ammonium group, a halogen atom-containing group, a sulfonic acid group, and the like, and groups derived from these functional groups, such as an ester group. And the like. Such functional groups are introduced before or after hydrogenation of the hydrogenated diene-based copolymer (b), depending on their type. In the present invention, the hydrogenated diene copolymer can be used alone or in combination of two or more.

As the phosphoric ester compound (c) used in the present invention, a phosphoric ester and its derivative can be suitably used. Phosphate compounds include, for example, phosphates, phosphate salts, alkyl phosphates,
Alkyl phosphates, alkyl ether phosphates, alkyl ether phosphates, alkylphenol phosphates, alkylphenol phosphates, alkylphenol ether phosphates, alkylphenol ether phosphates, higher alcohol phosphates, higher alcohols And phosphoric acid ester salts. Of these, alkyl phosphates, alkyl phosphates, alkyl ether phosphates, and alkyl ether phosphates are preferred. 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. Ether phosphates,
Examples of stearyl ether phosphates and alkyl ether type phosphates include potassium lauryl ether phosphate and potassium stearyl ether phosphate. The phosphoric ester compound of the present invention (c)
Examples thereof include a monoester type, a diester type, and a triester type, and they can be used alone or as a mixture of two or more.

The pressure-sensitive adhesive layer (d) of the present invention comprises the hydrogenated diene copolymer (b) and the phosphate compound (c). The pressure-sensitive adhesive layer (d) is a hydrogenated diene copolymer (b)
The phosphoric acid ester compound (c) 0.0
It is 1 to 10 parts by weight, preferably 0.1 to 5 parts by weight.
If the amount is less than 0.01 part by weight, the adhesive strength after long-term sticking will increase remarkably, and the peelability may decrease. If the amount exceeds 10 parts by weight, adhesive residue is left on the adherend during peeling, which is not preferable. The pressure-sensitive adhesive layer (d) of the present invention may contain a tackifier resin, an olefin-based resin, and a stabilizer in addition to the hydrogenated diene-based copolymer (b) and the phosphate compound (c). As the tackifier, those which are compatible with the hydrogenated diene-based copolymer (b) and improve the adhesive strength are preferable. For example, aliphatic hydrocarbon resins, terpene resins, cumarone-indene resins,
Aromatic hydrocarbon resins, rosin resins, phenolic resins and the like are preferably used.

As the olefin resin, one kind or two kinds
A resin obtained by polymerizing at least one kind of monoolefin by either a high-pressure method or a low-pressure method, and is preferably polyethylene, polypropylene, polybutene-1, or poly-4.
-Methylpentene-1 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. .
Further, if necessary, an inorganic filler such as talc, silica, charcoal and the like, and an organic filler such as carbon fiber and amide fiber may be contained. The mixing of the hydrogenated diene copolymer (b) and the phosphate compound (c) of the present invention can be performed using a mixer such as a Banbury mixer, a roll mill, an extruder or the like. It is preferred to melt-knead the mixture.

The production of the pressure-sensitive adhesive film and sheet having good weather resistance of the present invention is carried out, for example, as follows. (A) a method in which an adhesive layer extruded using an extruder is heat-bonded onto a base material layer, (b) a method in which a co-extrusion type inflation molding machine or a T-die extrusion molding machine is used to directly form a laminate, (c) ) For example, it can be manufactured by laminating by a known method such as a method of extruding and laminating an adhesive layer on one surface of the base material layer by the method (a). The die of the extruder used in the method (b) may be either a multi-manifold type or a feed block type. When using a thermoplastic resin for the base material layer (a),
Among these methods, the method (b) of laminating by coextrusion is preferable. In the method (b), a two-layer co-extrusion method in which an adhesive layer is laminated on one surface of a base material layer, a three-layer co-extrusion method in which an adhesive layer is laminated on one surface of an outermost layer, and Multi-layer extrusion of more than one layer can be employed. The pressure-sensitive adhesive film of the present invention has a pressure-sensitive adhesive layer laminated on one surface of a substrate layer. When two or more substrate layers are laminated, each layer may be the same or different. On one side of the material layer,
Two or more pressure-sensitive adhesive layers can be laminated. The thickness of the pressure-sensitive adhesive film of the present invention is appropriately selected depending on the desired properties and applications of the pressure-sensitive adhesive film and sheet having good weather resistance. From the viewpoint of moldability and strength, the thickness is preferably 10 μm or more. Preferably, it is not less than 20 μm.

[0017]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples unless it exceeds the gist thereof.
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. Initial adhesive strength The initial adhesive strength was measured according to the JIS Z-0237 method for the prepared weather-resistant pressure-sensitive adhesive film and sheet.
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. Moldability A molded product was molded and visually evaluated. ；: Good molding processability ×: poor weathering processability Weathering acceleration test After adhering a weatherable pressure-sensitive adhesive film and sheet prepared on SUS304 steel plate according to JIS Z-0237 method, carbon arc is used as a light source. Black panel temperature 63 ° C, rainfall 1 with sunshine weather meter
After exposure under the conditions of 8 min / 120 min and processing time of 300 hr, a peeling angle of 180 ° and a peeling speed of 300 mm /
The adhesion was measured under the condition of min. The adherend surface that had been peeled off in the adhesive residue weathering acceleration test was visually evaluated. ○: No adhesive residue ×: Adhesive residue

The components used in the formulations of the examples and comparative examples are as follows. I, (a) component (a-1) polyethylene (YF3, manufactured by Mitsubishi Chemical Corporation)
0) (A-2) Polypropylene double-sided high-quality paper (thickness 80)
μm) (A-3) Polyethylene foam sheet (150 μm thick)
m) II, (b) Component The hydrogenated diene copolymers (b-1) to (b-
3) was synthesized. The hydrogenated diene copolymer (b-4) is
Hydrogenated styrene-ethylene-butylene manufactured by Shell Co., Ltd.
Styrene block copolymer (SEBS) (trade name Clayton G-1652). Table 1 summarizes the microstructure, number average molecular weight, and hydrogenation rate of these hydrogenated diene copolymers.

[0019]

[Table 1]

III, (C) Component (C-1) Lauryl phosphate potassium salt (manufactured by Takemoto Yushi Co., Ltd., JAS-101) (C-2) Stearyl phosphate ester potassium salt (Takemoto Yushi Co., Ltd., JSR -105) (C-3) Stearyl ether phosphate potassium salt (Sofon GF-2 manufactured by Toho Chemical Co., Ltd.) (C-4) Lauryl phosphate (Nikko Chemicals Co., Ltd., Nikkor Phosten HLP)

Examples 1 to 6 A base material layer having a thickness of 45 μm comprising the above-mentioned component (A-1) and a pressure-sensitive adhesive layer having a thickness of 15 μm having a composition shown in Table 2 were prepared.
Extrusion molding machine (Modern Machinery Co., Ltd., base material layer: 65 m, capable of forming a pressure-sensitive adhesive film having a total thickness of 60 μm into a two-layer film having a T-die with a feed block.
mφ, for surface layer: 50 mmφ) and extrusion temperature 24
Co-extrusion was performed at 0 ° C. and a cooling roll temperature of 20 ° C. The obtained pressure-sensitive adhesive film was evaluated. As a result, the obtained pressure-sensitive adhesive film had excellent initial adhesive strength and moldability, and had good peelability after the weather resistance acceleration test and no adhesive residue. Table 2 shows the evaluation results.

[0022]

[Table 2]

Example 7 A 15 μm-thick pressure-sensitive adhesive layer having the composition shown in Table 2 was extruded on a base material layer composed of the component (A-2) and provided with a T-die (manufactured by Modern Machinery Co., Ltd.). : 50 mmφ), and extrusion-laminated under the conditions of an extrusion temperature of 240 ° C and a cooling roll temperature of 20 ° C to obtain a pressure-sensitive adhesive sheet having a total thickness of 95 µm. About the obtained pressure-sensitive adhesive sheet,
An evaluation was performed. As a result, the obtained pressure-sensitive adhesive sheet was excellent in initial adhesive strength and moldability, and had good releasability after a weather resistance acceleration test and no adhesive residue. Table 2 shows the evaluation results. Example 8 A pressure-sensitive adhesive layer having a total thickness of 165 μm under the same conditions as in Example 7 and a 15 μm-thick pressure-sensitive adhesive layer having the composition shown in Table 2 was formed on the base material layer composed of the component (A-3). A functional sheet was obtained.
Various evaluations were performed on the obtained pressure-sensitive adhesive sheet. As a result, the obtained pressure-sensitive adhesive sheet was excellent in initial adhesive strength and moldability, and had good releasability after a weather resistance acceleration test and no adhesive residue. Table 2 shows the evaluation results. Comparative Examples 1 and 2 A pressure-sensitive adhesive film having a total thickness of 60 μm, comprising a 45 μm-thick base material layer composed of the component (A) and a 15 μm-thick pressure-sensitive adhesive layer having the composition shown in Table 2, It produced under the same conditions as Examples 1-6, and evaluated. As a result, the pressure-sensitive adhesive film of Comparative Example 1 is excellent in initial adhesive strength and moldability, but is out of the range of the present invention, so that the adhesive strength after the weathering acceleration test is increased and good peelability is obtained. I couldn't. Comparative Example 2
Since the pressure-sensitive adhesive film was out of the range of the present invention, good initial adhesive strength and good moldability could not be obtained. Also,
Since a good initial adhesive strength was not obtained, a weather resistance acceleration test could not be performed. Table 2 shows the evaluation results.

[0024]

The pressure-sensitive adhesive film and sheet having good weather resistance according to the present invention can be manufactured by extrusion molding, have excellent weather resistance and molding processability, have an appropriate adhesive strength, and have good peeling properties. A good pressure-sensitive adhesive film was obtained, and a surface protection film, adhesive tape, adhesive label, adhesive sheet, assembly used to prevent scratches on steel plates, painted steel plates, decorative steel plates, glass plates, resin plates, etc. It can be used for such purposes and has great industrial value.

Claims (1)

[Claims] 1. The base material layer (a) and at least one surface of the base material layer, the following (c):
Pressure-sensitive adhesive laminate having pressure-sensitive adhesive layer (d) containing from 0.01 to 10 parts by weight (b) Condensed diene portion of a polymer mainly composed of a random copolymerized portion of a conjugated diene compound and an aromatic vinyl compound Hydrogenated diene polymer with double bonds hydrogenated (c) Phosphate compound