JP6103924B2 - Adhesive laminate - Google Patents

Description

  The present invention relates to a pressure-sensitive adhesive laminate including a pressure-sensitive adhesive layer comprising a polyolefin-based resin composition layer and an acrylic pressure-sensitive adhesive composition.

  Contains an acrylic polymer because of its excellent transparency, weather resistance, and durability as a pressure-sensitive adhesive used in pressure-sensitive adhesive products that have a pressure-sensitive adhesive layer on the surface of at least a part of the base material layer, such as protective films and pressure-sensitive adhesive tapes. Solution type pressure-sensitive adhesives are widely used (see Patent Document 1). However, when a solution-type pressure-sensitive adhesive is used, a step of dissolving the pressure-sensitive adhesive in a solvent and a step of removing the solvent by drying are required, and the manufacturing process of the pressure-sensitive adhesive product becomes complicated. Therefore, there are problems such as an increase in cost and an increase in environmental load. In addition, as the acrylic polymer, an acrylic random copolymer obtained by radical polymerization is conventionally used, but the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is generally 2. It is as wide as about 0.0 to 5.0, and the adhesive residue on the adherend is likely to be generated due to containing a low molecular weight component at a certain ratio. And it had the problem that it was not suitable for the use which needs to repeat adhesion and peeling especially.

  On the other hand, a pressure-sensitive adhesive film and a pressure-sensitive adhesive sheet, which are produced by a coextrusion molding method and are laminated with a base material layer made of polyolefin resin and a pressure-sensitive adhesive layer made of an acrylic block copolymer, have been proposed. In the coextrusion molding method, the above-mentioned pressure-sensitive adhesive product can be produced at a lower cost than using a solution-type pressure-sensitive adhesive. However, the polyolefin resin, which is a nonpolar material, and the acrylic block copolymer, which is a polar material, have a weak interlayer strength, which may cause a problem of delamination. In order to solve this problem, for example, an adhesive layer is provided between the base material layer and the pressure-sensitive adhesive layer (see Patent Document 2), ionizing radiation is irradiated (see Patent Document 3), and the acrylic block copolymer is polyolefinized. A method of blending a resin (see Patent Document 4) has been proposed. However, the resin disclosed as being used for the adhesive layer in Patent Document 2 is inferior in coextrusion processability with an acrylic block copolymer, and there is a problem that the thickness of the resulting pressure-sensitive adhesive product varies. Since the method of Patent Document 3 irradiates ionizing radiation from the adhesive layer side, surface roughness of the adhesive layer may occur. In addition, as in Patent Document 4, when an acrylic block copolymer and a polyolefin resin are mixed, the kneading state tends to be insufficient due to differences in compatibility and fluidity, and the adhesive performance tends to become unstable. Yes, there is room for improvement.

JP 2008-256748 A JP 2009-241348 A JP 2012-057040 A JP 2012-102172 A JP-A-6-093060 Japanese National Patent Publication No. 5-507737 JP-A-11-335432

Macromolecular Chemistry and Physics, 2000, 201, p. 1108 to 1114

  Accordingly, an object of the present invention is to provide a pressure-sensitive adhesive laminate having good coextrusion processability, excellent adhesive properties, hardly delamination, and less sticking when rolled.

According to the present invention, the above object is
[1] A pressure-sensitive adhesive laminate comprising a pressure-sensitive adhesive layer (B) comprising a polyolefin-based resin composition layer (A) and an acrylic pressure-sensitive adhesive composition, and produced by coextrusion molding;
[2] The acrylic pressure-sensitive adhesive composition has at least one polymer block (i-1) composed of methacrylic acid ester units and at least one polymer block (i-2) composed of acrylate ester units. And an acrylic block copolymer (I) having a weight average molecular weight (Mw) of 30,000 to 300,000;
[3] The polyolefin-based resin composition layer (A) includes a polyolefin-based resin composition layer (A-1) having a tensile elastic modulus at 23 ° C. of 300 to 1800 MPa, and a polyolefin-based polymer having a polar group. Containing a polyolefin resin composition layer (A-2) comprising a polyolefin resin composition having a melt flow rate of 5.0 to 50 g / 10 min measured at 190 ° C. and 2.16 kg, A-2) and the pressure-sensitive adhesive layer (B) are adjacent, [1] or [2] the pressure-sensitive adhesive laminate;
[4] Extension viscosity ηEx (Pa · s) at an extension rate of 10 (1 / s) measured at 190 ° C. of the acrylic pressure-sensitive adhesive composition constituting the adhesive layer (B) and an extension rate measured at 190 ° C. The pressure-sensitive adhesive laminate according to the above [1] to [3], wherein the ratio (ηEx / ηEy) of the extensional viscosity ηEy (Pa · s) at 1000 (1 / s) is 15 or less;
[5] Elongation viscosity ηEa (Pa · s) at an elongation rate of 10 (1 / s) measured at 190 ° C. of the polyolefin resin composition constituting the polyolefin resin composition layer (A-2), and 190 ° C. The pressure-sensitive adhesive laminate according to [3] or [4], wherein the ratio (ηEa / ηEb) of the extensional viscosity ηEb (Pa · s) at an extension rate of 1000 (1 / s) measured in step 1 is 15 or less;
[6] The difference between ηEa / ηEb of the polyolefin resin composition constituting the polyolefin resin composition layer (A-2) and ηEx / ηEy of the acrylic adhesive composition constituting the adhesive layer (B) The pressure-sensitive adhesive laminate according to [3] to [5], which has an absolute value of 10 or less.
[7] The pressure-sensitive adhesive laminate according to [2] to [6], wherein the content of the polymer block (i-1) in the acrylic block copolymer (I) is 5 to 50% by weight;
[8] The above [2] to [2], wherein the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the acrylic block copolymer (I) is 1.0 to 2.0. 7] an adhesive laminate;
[9] The acrylic ester unit constituting the polymer block (i-2) of the acrylic block copolymer (I) is represented by the general formula CH ₂ = CH-COOR ¹ (W) (wherein R ¹ is Acrylic acid ester (a) and general formula CH ₂ ═CH—COOR ² (X) (wherein R ² represents an organic group having 7 to 12 carbon atoms) And the mass ratio (a) / (b) of the acrylic ester (a) and the acrylic ester (b) is 90/10 to 10/90. [2]-[8] adhesive laminates;
[10] The pressure-sensitive adhesive laminate according to [9], wherein the acrylic ester (a) is butyl acrylate;
[11] The pressure-sensitive adhesive laminate according to [9] or [10], wherein the acrylic ester (b) is 2-ethylhexyl acrylate;
[12] The pressure-sensitive adhesive laminate according to [3] to [11], wherein the polyolefin-based resin composition layer (A-1) is made of a polypropylene-based resin composition;
[13] The polyolefin resin composition layer (A-2) contains at least one resin selected from an ethylene-acrylic acid ester copolymer, an ethylene-methacrylic acid copolymer, and a maleic anhydride-modified olefin resin. [3] to [12], an adhesive laminate comprising the composition to be used;
[14] A protective film comprising the adhesive laminate according to any one of [1] to [13];
[15] An adhesive tape comprising the adhesive laminate according to any one of [1] to [13] above;
[16] A label comprising the adhesive laminate according to any one of [1] to [13] above;
[17] A polyolefin resin composition layer (A-1) having a tensile modulus of elasticity at 23 ° C. of 300 to 1800 MPa and an olefin polymer containing a polar group, measured at 190 ° C. and 2.16 kg. A polyolefin resin composition layer (A-2) comprising a polyolefin resin composition having a melt flow rate of 5.0 to 50 g / 10 min, and an acrylic pressure-sensitive adhesive composition having ηEx / ηEy of 15 or less. The adhesive layer (B) is coextruded so that the polyolefin resin composition layer (A-1), the polyolefin resin composition layer (A-2) and the adhesive layer (B) are adjacent to each other [3] to [3] 13] The manufacturing method of the adhesion laminated body of;
Is achieved by providing

  According to the present invention, it is possible to provide a pressure-sensitive adhesive laminate that has good processability by the melt coextrusion method, has excellent adhesive properties, is difficult to delaminate, and has less sticking when rolled.

  The pressure-sensitive adhesive laminate of the present invention includes a polyolefin-based resin composition layer (A) and a pressure-sensitive adhesive layer (B) made of an acrylic pressure-sensitive adhesive composition.

  The polyolefin resin composition layer (A) is a layer made of a polyolefin resin composition. Examples of the polyolefin resin contained in the polyolefin resin composition include olefin polymers such as olefin homopolymers or copolymers; olefin polymers containing polar groups, and the like.

  The olefin polymer may contain unsaturated monomers other than olefins. Moreover, the monomer unit constituting the polymer may have a halogen group, a sulfone group, or a silyl group. Examples of the olefin polymer include polyethylene resins such as polyethylene, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, chlorinated polyethylene; polypropylene, propylene-ethylene random copolymer, Ethylene and propylene copolymers such as propylene-ethylene block copolymers, ethylene-propylene-nonconjugated diene copolymers, polypropylene resins such as chlorinated polypropylene; poly-1-butene, polyisobutylene, polymethylpentene, Examples thereof include (co) polymers of cyclic olefins. These may be used individually by 1 type and may use 2 or more types together.

  The polar group of the olefin polymer containing a polar group includes an acid anhydride group derived from maleic anhydride, succinic anhydride, fumaric anhydride, etc .; a carboxyl group derived from acrylic acid, methacrylic acid, etc. Carboxylic acid groups; ester groups derived from acrylic acid esters and methacrylic acid esters; acyloxy groups derived from vinyl acetate and the like; silyl groups; hydroxyl groups; glycidyl groups and the like. Examples of the olefin polymer containing a polar group include acid anhydrides such as maleic anhydride, succinic anhydride, and fumaric anhydride; carboxylic acids such as acrylic acid and methacrylic acid, and metal salts thereof (examples of metals: Na); (meth) acrylic acid esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl methacrylate; vinyl acetate, etc. Copolymers of polar group-containing monomers and olefins, or modified olefins obtained by addition polymerization or graft polymerization of olefin-based polymers with silyl group-containing compounds such as vinyl silane, maleic anhydride, maleic acid, and glycidyl methacrylate A polymer etc. are mentioned. The modified olefin polymer is obtained by, for example, melting an olefin polymer in the presence of a radical initiator and adding a silyl group-containing compound such as maleic anhydride, maleic acid, glycidyl methacrylate, vinyl silane, and reacting them. It is done.

  Examples of the copolymer of a monomer containing a polar group and an olefin include, for example, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-n-propyl acrylate copolymer, Ethylene-isopropyl acrylate copolymer, ethylene-n-butyl acrylate copolymer, ethylene-t-butyl acrylate copolymer, ethylene-isobutyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene -Ethyl methacrylate copolymer, ethylene-n-propyl methacrylate copolymer, ethylene-isopropyl methacrylate copolymer, ethylene-n-butyl methacrylate copolymer, ethylene-t-butyl methacrylate copolymer, Ethylene-isobutyl methacrylate copolymer, ethylene- (meth) acrylic acid copolymer And its metal salt, ethylene-maleic anhydride copolymer, ethylene-butene-maleic anhydride copolymer, ethylene-propylene-maleic anhydride copolymer, ethylene-hexene-maleic anhydride copolymer Polymer, ethylene-octene-maleic anhydride copolymer, propylene-maleic anhydride copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-vinyl acetate-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl Examples include methacrylate copolymers.

  Examples of the modified olefin polymer include modified maleic anhydride such as polypropylene, polyethylene, ethylene-ethyl acrylate copolymer, SBS, SIS, SEBS, SEPS, ethylene-ethyl acrylate copolymer, and modified vinyl silane. A polyolefin-vinyl polymer graft copolymer, a copolymer obtained by graft-copolymerizing ethylene propylene rubber with glycidyl methacrylate, and the like.

  The polyolefin-based resin composition layer (A) is preferably composed of a polyolefin-based resin composition having a melting point of 90 ° C. or higher, and a polyolefin-based resin composition having a melting point of 100 ° C. or higher, from the viewpoint of coextrusion processability. It is preferable. Here, the melting point refers to the peak top temperature of the absorption heat curve measured by differential scanning calorimetry (DSC).

  The polyolefin-based resin composition may appropriately contain various additives such as a light stabilizer, an ultraviolet absorber, an antioxidant, a filler, and a lubricant as necessary. Examples of the lubricant include erucic acid amide, ethylene bis oleyl amide, oleic acid amide, methylene bis stearic acid amide and the like. Examples of the ultraviolet absorber include benzotriazole-based, benzophenone-based, and salicylic acid ester-based compounds. Examples of the light stabilizer include phenol-based, phosphorus-based, and hindered amine-based compounds.

  The polyolefin-based resin composition layer (A) has a tensile elastic modulus of 300 to 1800 MPa at 23 ° C. and a tensile speed of 300 mm / min from the viewpoint of coextrusion processability, adhesive properties, and delamination suppression of the resulting adhesive laminate. A polyolefin-based resin composition layer (A-1) (hereinafter sometimes simply referred to as a polyolefin-based resin composition layer (A-1)), an olefin-based polymer containing a polar group, and 190 A polyolefin resin composition layer (A-2) (hereinafter, simply referred to as a polyolefin resin composition layer (A-) comprising a polyolefin resin composition having a melt flow rate measured at 2.16 kg at 5 ° C. and 5 to 50 g / 10 min. 2), which may be referred to as 2).

The polyolefin resin composition constituting the polyolefin resin composition layer (A-1) has a tensile elastic modulus of 300 to 1800 MPa and preferably 800 to 1500 MPa at 23 ° C. and a tensile speed of 300 mm / min. When the tensile modulus is smaller than the above range, the flexibility of the obtained pressure-sensitive adhesive laminate is increased, and the handling properties in the bonding process with the adherend are deteriorated. When the tensile elastic modulus is larger than the above range, there is a problem that defects such as cracks and cracks occur in the process of bonding to the adherend and peeling from the adherend, and the adherend is damaged.
Here, the tensile elastic modulus of the polyolefin-based resin composition is a value measured under conditions of 23 ° C. and a tensile speed of 300 mm / min in accordance with the method described in ISO527-3.

  From the viewpoint of heat resistance, the melting point of the polyolefin resin composition constituting the polyolefin resin composition layer (A-1) is preferably 100 ° C. or higher, and more preferably 120 ° C. or higher.

  The polyolefin resin contained in the polyolefin resin composition constituting the polyolefin resin composition layer (A-1) is the one exemplified as the polyolefin resin contained in the polyolefin resin composition layer (A). Any of the polyolefin-based resin compositions may be used as long as the tensile elastic modulus at 23 ° C. and a tensile speed of 300 mm / min satisfies 300 to 1800 MPa, or one kind may be used alone, or two or more kinds may be used in combination. . Of these, polyethylene resins, polypropylene resins, and mixtures thereof are preferable from the viewpoint of balance between cost and physical properties, polypropylene resins are more preferable, and polypropylene is particularly preferable from the viewpoints of heat resistance and handling properties.

The polyolefin resin composition constituting the polyolefin resin composition layer (A-2) contains an olefin polymer containing a polar group.
Examples of the polar group include acid anhydrides derived from maleic anhydride, succinic anhydride, fumaric anhydride, and the like from the viewpoint of adhesiveness or adhesion to the pressure-sensitive adhesive layer (B) made of an acrylic pressure-sensitive adhesive composition. Carboxyl group and carboxylate group derived from acrylic acid, methacrylic acid, etc .; ester group derived from acrylic ester, methacrylic ester, etc .; acyloxy group derived from vinyl acetate, etc .; silyl group; hydroxyl group; glycidyl Groups and the like are preferred. Among these, a carboxyl group is preferable from the viewpoint of handleability. Examples of the olefin polymer containing the polar group include those similar to the olefin polymer containing the polar group exemplified for the polyolefin resin contained in the polyolefin resin composition layer (A). .
The olefin constituting the olefin polymer containing the polar group is preferably composed mainly of propylene or ethylene. The said olefin polymer containing a polar group may be used individually by 1 type, and may use 2 or more types together. From the viewpoint of adhesiveness with the pressure-sensitive adhesive layer (B), the content of the structural unit having a polar group in the olefin polymer containing the polar group is preferably 1 to 50% by mass, and 10 to 50% by mass. Some are more preferred.

  The polyolefin resin composition constituting the polyolefin resin composition layer (A-2) preferably contains only an olefin polymer containing a polar group as the polymer component. As long as the effect is not impaired, another polymer may be further contained as necessary. Examples of other polymers include olefin polymers exemplified as the polyolefin resin contained in the polyolefin resin composition layer (A); polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, AS resin, ABS. Resin, AES resin, AAS resin, ACS resin, MBS resin and other styrene resins; styrene-methyl methacrylate copolymer; PMMA resin, acrylic block copolymer and other acrylic resins; polyethylene terephthalate, polybutylene terephthalate, Polyester resins such as polylactic acid; polyamide resins such as nylon 6, nylon 66, polyamide elastomer; ester polyurethane elastomer, ether polyurethane elastomer, non-yellowing ester polyurethane elastomer, non-yellowing carbon Polyurethane resins such as polyurethane-based polyurethane elastomers; polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinylidene fluoride, modified polyphenylene ether, polyphenylene sulfide, silicone rubber modified resin, etc. It is done. Among these, from the viewpoint of adhesiveness with the polyolefin resin composition layer (A-1) and the adhesive layer (B) made of the acrylic adhesive composition, a styrene-methyl methacrylate copolymer and an acrylic resin are used. preferable.

  From the viewpoint of coextrusion moldability, the extension viscosity ηEa (Pa · s) at an extension rate of 10 (1 / s) measured at 190 ° C. of the polyolefin resin composition constituting the polyolefin resin composition layer (A-2). And the ratio (ηEa / ηEb) of the extensional viscosity ηEb (Pa · s) at an extension rate of 1000 (1 / s) measured at 190 ° C. is preferably 15 or less, more preferably 10 or less, More preferably, it is 7 or less. In addition, the measuring method of (eta) Ea and (eta) Eb is based on the method shown in the Example mentioned later.

  The pressure-sensitive adhesive layer (B) is composed of at least one polymer block (i-1) composed of methacrylic acid ester units (hereinafter sometimes simply referred to as polymer block (i-1)) and acrylate ester units. An acrylic pressure-sensitive adhesive composition containing an acrylic block copolymer (I) having at least one polymer block (i-2) or less, which may be simply referred to as a polymer block (i-2)) It is preferable that it is comprised from a thing. The weight average molecular weight (Mw) of the acrylic block copolymer (I) is usually preferably in the range of 30,000 to 300,000, and more preferably in the range of 45,000 to 150,000. When the weight average molecular weight (Mw) of the acrylic block copolymer (I) is smaller than the above range, the melt viscosity of the acrylic block copolymer (I) becomes extremely small, the take-off property is inferior, and the coextrusion molding process is performed. Becomes difficult. When the weight average molecular weight (Mw) of the acrylic block copolymer (I) is larger than the above range, the melt viscosity of the acrylic block copolymer (I) becomes extremely large, and a molded product obtained by coextrusion molding processing. The surface of may be rough. In addition, when coextrusion molding is performed by the T-die method, the spread to both ends is insufficient, and a good pressure-sensitive adhesive laminate may not be obtained. In addition, from the viewpoint of adhesive properties such as improvement in cohesive strength of the adhesive layer (B) comprising the acrylic adhesive composition, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the acrylic block copolymer (I) Ratio (Mw / Mn) is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, still more preferably 1.0 to 1.5, It is especially preferable that it is 1.0-1.3.

  Examples of the methacrylic acid ester that is a constituent unit of the polymer block (i-1) include, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid. sec-butyl, tert-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, isobornyl methacrylate, methacrylic acid Methacrylic acid ester having no functional group such as phenyl and benzyl methacrylate; methoxyethyl methacrylate, ethoxyethyl methacrylate, diethylaminoethyl methacrylate, methacrylate 2-hydroxyethyl methacrylate, 2-aminoethyl methacrylate, glycidyl methacrylate, and methacrylic acid esters having a functional group such as tetrahydrofurfuryl methacrylate.

  Among these, from the viewpoint of improving the transparency, heat resistance, and durability of the acrylic pressure-sensitive adhesive composition containing the obtained acrylic block copolymer (I) or the acrylic block copolymer (I), Methacrylic acid ester having no functional group is preferable, methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, and phenyl methacrylate are more preferable, and methyl methacrylate is more preferable. Polymer block (i-1) may be comprised from 1 type of these methacrylic acid ester, or may be comprised from 2 or more types. Moreover, the acrylic block copolymer (I) preferably contains two or more polymer blocks (i-1) from the viewpoint of enhancing durability. In that case, these polymer blocks (i-1) may be the same or different.

  Although the weight average molecular weight (Mw) of a polymer block (i-1) is not specifically limited, Usually, it exists in the range of 1000-50000, and it is more preferable that it exists in the range of 4000-20000. When the weight average molecular weight (Mw) of the polymer block (i-1) is smaller than this range, the resulting acrylic block copolymer (I) or an acrylic containing the acrylic block copolymer (I) In some cases, the cohesive force of the adhesive composition is insufficient. Moreover, when the weight average molecular weight (Mw) of a polymer block (i-1) is larger than this range, the melt viscosity of the acrylic adhesive composition obtained becomes high, and acrylic block copolymer (I) The productivity and coextrusion processability may be inferior. The proportion of the methacrylic acid ester unit contained in the polymer block (i-1) is preferably 60% by mass, more preferably 80% by mass or more, and still more preferably 90% by mass or more in the polymer block (i-1). .

  The content of the polymer block (i-1) in the acrylic block copolymer (I) is preferably 5 to 50% by mass. An acrylic pressure-sensitive adhesive having excellent adhesiveness and containing the acrylic block copolymer (I) or the acrylic block copolymer (I) in a form that is easy to handle (eg, pellets) The content of the polymer block (i-1) is preferably 10 to 45% by mass, and more preferably 15 to 40% by mass from the viewpoint that the composition can be supplied.

  Examples of the acrylate unit constituting the polymer block (i-2) include n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, Functional groups such as n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, decyl acrylate, isobornyl acrylate, lauryl acrylate, phenyl acrylate, and benzyl acrylate Acrylic acid ester not present: methoxyethyl acrylate, ethoxyethyl acrylate, diethylaminoethyl acrylate, 2-hydroxyethyl acrylate, 2-aminoethyl acrylate, glycidyl acrylate, tetrahydic acrylate Rofurufuriru, acrylic acid esters having a functional group such as phenoxyethyl acrylate. Among these, from the viewpoint of improving the transparency, flexibility, cold resistance, and low temperature characteristics of the acrylic pressure-sensitive adhesive composition containing the resulting acrylic block copolymer (I), acrylic acid having no functional group Esters are preferred. These may be used alone or in combination of two or more.

When two or more kinds of acrylic esters constituting the polymer block (i-2) are used in combination, the transparency, flexibility and cold resistance of the acrylic pressure-sensitive adhesive composition containing the resulting acrylic block copolymer (I) gender, to improve low temperature properties, and from the viewpoint of improving co-extrusion processability, the general formula ^{_{CH 2 = CH-COOR 1 (}} a) ( wherein, ^{R 1} represents an organic group having 4 to 6 carbon atoms) An acrylate ester (a) (hereinafter simply referred to as an acrylate ester (a)) and a general formula CH ₂ ═CH—COOR ² (b) (wherein R ² is an organic group having 7 to 12 carbon atoms) It is preferable to use together an acrylate ester (b) (hereinafter simply referred to as an acrylate ester (b)).

  Examples of the acrylate ester (a) include n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, and cyclohexyl acrylate. Acrylic acid ester having no functional group such as phenyl acrylate; methoxyethyl acrylate, ethoxyethyl acrylate, diethylaminoethyl acrylate, 2-hydroxyethyl acrylate, 2-aminoethyl acrylate, glycidyl acrylate, acrylic Examples thereof include acrylic acid esters having a functional group such as acid tetrahydrofurfuryl. Among these, acrylate esters such as n-butyl acrylate and n-hexyl acrylate are more preferable. These may be used alone or in combination of two or more.

  Examples of the acrylate ester (b) include 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, decyl acrylate, isobornyl acrylate, lauryl acrylate, benzyl acrylate, phenoxyethyl acrylate, and the like. It is done. Among these, from the viewpoint of improving the transparency, flexibility, cold resistance, and low temperature characteristics of the acrylic block copolymer (I) or the acrylic pressure-sensitive adhesive composition containing the acrylic block copolymer (I). Acrylic acid esters such as 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, lauryl acrylate, and phenoxyethyl acrylate are preferred. In addition, acrylic acid is superior in that it has excellent adhesive properties (tack, adhesive force, etc.) at low temperatures (10 to -40 ° C.) and exhibits stable adhesive force under a wide range of peeling speed conditions. 2-ethylhexyl, n-octyl acrylate, and isooctyl acrylate are more preferable. These may be used alone or in combination of two or more.

  The mass ratio (a) / (b) of the acrylate ester (a) and the acrylate ester (b) in the polymer block (i-2) imparts excellent adhesive properties and is further in phase with the tackifier resin. From the viewpoint of enhancing the capacity, the mass ratio (a) / (b) is preferably 90/10 to 10/90, and more preferably 60/40 to 40/60. In addition, mass ratio of acrylic ester (a) and acrylic ester (b) is calculated | required by the method as described in the below-mentioned Example.

When two or more acrylates constituting the polymer block (i-2) are used in combination, examples of the combination include n-butyl acrylate / 2-ethylhexyl acrylate, n-butyl acrylate / octyl acrylate. , N-hexyl acrylate / 2-ethylhexyl acrylate, n-butyl acrylate / lauryl acrylate, n-butyl acrylate / benzyl acrylate, n-butyl acrylate / [2-ethylhexyl acrylate / lauryl acrylate] Etc. At this time, it is more preferable that the difference in solubility parameter between the acrylic ester (a) and the acrylic ester (b) to be used is 1.0 to 2.5 (MPa) ^1/2 . The solubility parameters are described in “POLYMER HANDBOOK Forth Edition”, pages 675 to 714 (issued by Wiley Interscience, 1999) and “Polymer Engineering and Science”, 1974, pages 14 to 15; It can be calculated by the method described. Moreover, when the said acrylic block copolymer (I) contains two or more polymer blocks (i-2), the combination of the acrylate ester unit which comprises these polymer blocks (i-2) is , May be the same or different.

  The structure of the polymer block (i-2) may be, for example, a random copolymer of an acrylate ester (a) and an acrylate ester (b), a block copolymer, or a tapered block copolymer. It may be combined. When the acrylic block copolymer (I) contains two or more polymer blocks (i-2), the structures of the polymer blocks (i-2) may be the same or different. Good. Moreover, it is preferable that the ratio of the acrylate ester unit contained in polymer block (i-2) is 60 mass% or more in polymer block (i-2), and it is more preferable that it is 80 mass% or more. Preferably, it is 90 mass% or more.

  The polymer block (i-1) and the polymer block (i-2) may contain each other's components as long as the effects of the present invention are not impaired. Moreover, you may contain another monomer as needed. Examples of such other monomers include vinyl compounds having a carboxyl group such as (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, and fumaric acid; (meth) acrylamide, (meth) acrylonitrile, vinyl acetate Vinyl monomers having functional groups such as vinyl chloride and vinylidene chloride; aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene and m-methylstyrene; conjugated diene compounds such as butadiene and isoprene; Examples thereof include olefin compounds such as ethylene, propylene, isobutene and octene; and lactone monomers such as ε-caprolactone and valerolactone. When these are contained, the amount is usually preferably 40% by mass or less, more preferably 20% by mass or less, based on the total mass of the monomers used for each polymer block.

  The acrylic block copolymer (I) may have other polymer blocks as needed in addition to the polymer block (i-1) and the polymer block (i-2). Examples of such other polymer blocks include styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, acrylonitrile, methacrylonitrile, ethylene, propylene, isobutene, butadiene, isoprene, octene, vinyl acetate, anhydrous Examples thereof include a polymer block or copolymer block composed of maleic acid, vinyl chloride, vinylidene chloride and the like; a polymer block composed of polyethylene terephthalate, polylactic acid, polyurethane, polydimethylsiloxane, and the like. The polymer block also includes a hydrogenated polymer block containing a conjugated diene compound such as butadiene or isoprene.

  The method for producing the acrylic block copolymer (I) is not particularly limited as long as a polymer satisfying the conditions of the present invention concerning the chemical structure is obtained, and a method according to a known method can be adopted. In general, as a method of obtaining a block copolymer having a narrow molecular weight distribution, a method of living polymerizing monomers as constituent units is used. Examples of such living polymerization methods include a method of living polymerization using an organic rare earth metal complex as a polymerization initiator (see Patent Document 5), and an alkali metal or alkaline earth metal salt using an organic alkali metal compound as a polymerization initiator. A method of living anion polymerization in the presence of a mineral salt such as (see Patent Document 6), a method of living anion polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound (see Patent Document 7), An atom transfer radical polymerization method (ATRP) (see Non-Patent Document 1) and the like can be mentioned.

  Among the above production methods, a method for producing an acrylic block copolymer (I) by living anion polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound is an acrylic block copolymer obtained. The transparency of (I) is high, the residual monomer is small, the odor is suppressed, and when used as an acrylic pressure-sensitive adhesive composition, the generation of bubbles in the pressure-sensitive adhesive layer (B) can be suppressed, which is preferable. Furthermore, the molecular structure of the polymer block (i-1) is highly syndiotactic, and has the effect of increasing the heat resistance of the acrylic pressure-sensitive adhesive composition. Living polymerization is possible under relatively mild temperature conditions. In the production, the environmental load (mainly the electric power applied to the refrigerator for controlling the polymerization temperature) is also small.

As an organoaluminum compound, for example, the following general formula (Z)
AlR ³ R ⁴ R ⁵ (Z)
Wherein R ³ , R ⁴ and R ⁵ are each independently an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an aryl which may have a substituent. A group, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent or an N, N-disubstituted amino group, or R ³ is any of the groups described above, and R ⁴ and R ⁵ together form an aryleneoxy group which may have a substituent.) Can be mentioned.

  As the organoaluminum compound represented by the general formula (Z), isobutylbis (2,6-di-tert-butyl-4-methylphenoxy) aluminum is used from the viewpoint of high living property of polymerization and easy handling. And isobutylbis (2,6-di-tert-butylphenoxy) aluminum, isobutyl [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum and the like are preferable.

  Examples of the organic alkali metal compounds include alkyl lithium and alkyl dilithium such as n-butyl lithium, sec-butyl lithium, isobutyl lithium, tert-butyl lithium, n-pentyl lithium, and tetramethylene dilithium; phenyl lithium, p -Aryllithium and aryldilithium such as tolyllithium and lithium naphthalene; aralkyllithium and aralkyldilithium such as dilithium produced by the reaction of benzyllithium, diphenylmethyllithium, diisopropenylbenzene and butyllithium; lithium such as lithium dimethylamide Amides; lithium alkoxides such as methoxylithium and ethoxylithium are listed. These may be used alone or in combination of two or more. Of these, alkyl lithium is preferable because of high polymerization initiation efficiency, among which tert-butyl lithium and sec-butyl lithium are more preferable, and sec-butyl lithium is more preferable.

The living anion polymerization is usually performed in the presence of a solvent inert to the polymerization reaction. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloroform, methylene chloride, and carbon tetrachloride; ethers such as tetrahydrofuran and diethyl ether.
The acrylic block copolymer (I) is formed, for example, by adding a desired polymer block (polymer block (i-1), polymer block (i- 2) etc.) can be produced by repeating the desired number of times and then stopping the polymerization reaction. Specifically, for example, in the presence of an organoaluminum compound, a first step of polymerizing a monomer that forms the first polymer block with a polymerization initiator composed of an organic alkali metal compound, the second polymer block The weight obtained through a plurality of polymerization steps including a second step for polymerizing the monomer to be formed and a third step for polymerizing the monomer for forming the third polymer block as necessary. The acrylic block copolymer (I) can be produced by reacting the active terminal of the coal with alcohol or the like to stop the polymerization reaction. According to the method as described above, a binary block (diblock) copolymer comprising a polymer block (i-1) -polymer block (i-2) or a polymer block (i-1) -heavy A ternary block (triblock) copolymer comprising a polymer block (i-2) -polymer block (i-1), a polymer block (i-1) -polymer block (i-2) -polymer block A quaternary block copolymer comprising (i-1) -polymer block (i-2) can be produced.

  The polymerization temperature for conducting the living anion polymerization is preferably 0 to 100 ° C. when forming the polymer block (i-1), and preferably −50 to 50 ° C. when forming the polymer block (i-2). . When the polymerization temperature is lower than the above range, the progress of the reaction tends to be slow. On the other hand, when the polymerization temperature is higher than the above range, the deactivation of the living polymer terminal increases, the molecular weight distribution may be broadened, or a desired block copolymer may not be obtained.

  The acrylic pressure-sensitive adhesive composition containing the acrylic block copolymer (I) is within the range not impairing the effects of the present invention, other polymers, tackifying resins, softeners, plasticizers, heat stabilizers, One or more additives such as a light stabilizer, an antistatic agent, a flame retardant, a foaming agent, a coloring agent, a dyeing agent, a refractive index adjusting agent, a filler, and a curing agent may be further contained.

  Examples of the other polymer include acrylic resins such as polymethyl methacrylate and (meth) acrylate copolymer; polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, ethylene -Olefin resins such as methacrylic acid copolymer, maleic anhydride modified polyethylene, polypropylene, maleic anhydride modified polypropylene, polybutene-1, poly-4-methylpentene-1, polynorbornene; ethylene ionomer; polystyrene, styrene -Styrenic resins such as maleic anhydride copolymer, high impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin; styrene-methyl methacrylate copolymer; polyethylene terephthalate, polybutylene Polyester resins such as phthalates; Polyamides such as nylon 6, nylon 66, polyamide elastomers; Polycarbonates; Polyvinyl chloride; Polyvinylidene chloride; Polyvinyl alcohol; Ethylene-vinyl alcohol copolymers; Polyacetals; Polyvinylidene fluoride; Polyurethanes; Polyphenylene sulfide; silicone rubber modified resin; acrylic rubber; silicone rubber; styrene thermoplastic elastomer such as SEPS, SEBS, SIS; olefin rubber such as IR, EPR, EPDM, and the like.

  Examples of the tackifying resin include rosin such as gum rosin, tall oil rosin, and wood rosin; from the viewpoint of easy adjustment of tack, adhesive force and holding force; modified rosin such as hydrogenated rosin, disproportionated rosin, and polymerized rosin. Rosin; Rosin resins such as rosin, glycerin ester of modified rosin, rosin ester such as pentaerythritol ester; terpene resin mainly composed of α-pinene, β-pinene, dipentene, aromatic modified terpene resin, hydrogenated terpene Terpene resins such as resins and terpene phenol resins; (hydrogenated) aliphatic (C5) petroleum resins, (hydrogenated) aromatic (C9) petroleum resins, (hydrogenated) copolymers (C5 / C9) Type) petroleum resins, (hydrogenated) dicyclopentadiene type petroleum resins, alicyclic saturated hydrocarbon resins, etc. (hydrogenated) petroleum resins; poly α-methylstyrene α-methylstyrene / styrene copolymer, styrene monomer / aliphatic monomer copolymer, styrene monomer / α-methylstyrene / aliphatic monomer copolymer, styrene monomer Examples thereof include styrene resins such as a monomer copolymer and a styrene monomer / aromatic monomer copolymer; synthetic resins such as a coumarone-indene resin, a phenol resin, and a xylene resin. Among the above-mentioned tackifying resins, rosin resins, terpene resins, (hydrogenated) petroleum resins and styrene resins are preferable in terms of expressing high adhesive strength. Among them, rosins are preferable from the viewpoint of improving adhesiveness, and light resistance. From the viewpoint of suppressing deterioration, coloring, and generation of bubbles due to impurities, disproportionated or hydrogenated rosins purified by an operation such as distillation, recrystallization, or extraction are more preferable. These may be used alone or in combination of two or more. Moreover, about the softening point of the said tackifying resin, a 50-150 degreeC thing is preferable from the point which expresses high adhesive force.

Further, when the tackifier resin is contained, the content thereof is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the acrylic block copolymer (I) from the viewpoint of adhesive strength and durability. 3 to 70 parts by mass, more preferably 5 to 50 parts by mass, particularly preferably 5 to 40 parts by mass, and most preferably 5 to 35 parts by mass.
As the rosin resin, commercially available products such as Pine Crystal KE-100, Pine Crystal KE-311, Pine Crystal KE-359, Pine Crystal KE-604, Pine Crystal D-6250 (all manufactured by Arakawa Chemical Industries, Ltd.) are used. it can. Commercially available products such as Tamorol 901 (manufactured by Arakawa Chemical Industries, Ltd.) can be used as the terpene resin. As the styrene resin, commercially available products such as FTR6000 series and FTR7000 series (Mitsui Chemicals, Inc.) can be used.

  Examples of the plasticizer include dibutyl phthalate, di-n-octyl phthalate, bis-2-ethylhexyl phthalate, di-n-decyl phthalate, diisodecyl phthalate, and the like, bis-2-ethylhexyl adipate, di-n- Fatty acid esters such as adipate such as octyl adipate, sebacic acid ester such as bis-2-ethylhexyl sebacate, di-n-butyl sebacate, azelaic acid ester such as bis-2-ethylhexyl azelate; paraffin such as chlorinated paraffin Glycols such as polypropylene glycol; epoxy polymer plasticizers such as epoxidized soybean oil and epoxidized linseed oil; phosphate esters such as trioctyl phosphate and triphenyl phosphate; Phosphites such as wite; acrylic oligomers such as n-butyl poly (meth) acrylate and 2-ethylhexyl poly (meth) acrylate; polybutene; polyisobutylene; polyisoprene; process oil; naphthenic oil, etc. Can be mentioned. These may be used alone or in combination of two or more.

  Examples of the filler include inorganic fibers such as glass fibers and carbon fibers; organic fibers; inorganic fillers such as calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, and magnesium carbonate.

  Examples of the curing agent include a photocuring agent such as a UV curing agent and a thermosetting agent. For example, benzoin such as benzoin, α-methylolbenzoin, α-t-butylbenzoin; benzoin methyl ether, benzoin ethyl ether, benzoin- Benzoin ethers such as n-propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, α-methylol benzoin methyl ether, α-methoxybenzoin methyl ether, benzoin phenyl ether; benzophenone; 9,10-anthraquinone, 2-ethyl-9,10 Anthraquinone such as anthraquinone; benzyl; acetophenone such as 2,2-dimethoxy-1,2-diphenylethane-1-one (2,2-dimethoxy-2-phenylacetophenone); diacetyl Etc., and the like. One of these curing agents may be used alone, or two or more thereof may be used in combination. By containing a curing agent, the above-mentioned pressure-sensitive adhesive composition can be suitably used as a curable pressure-sensitive adhesive such as a UV curable hot melt pressure-sensitive adhesive.

  The method for producing the acrylic pressure-sensitive adhesive composition containing the acrylic block copolymer (I) is not particularly limited. For example, each component is mixed with a known kneader, a extruder, a mixing roll, a Banbury mixer, or the like. Or it can manufacture by mixing at the temperature in the range of 100-250 degreeC normally using a kneading apparatus, and the obtained acrylic adhesive composition can be heat-melted and used.

  The acrylic pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer (B) constituting the pressure-sensitive adhesive laminate of the present invention has an elongation viscosity ηEx (Pa · s) at 190 ° C. and an elongation speed of 10 (1 / s) measured at 190 ° C. The ratio (ηEx / ηEy) of the extensional viscosity ηEy (Pa · s) at an extension rate of 1000 (1 / s) measured in step 1 is preferably 15 or less, more preferably 10 or less, and 7 or less. It is preferable. By satisfying such properties, an adhesive laminate with little thickness variation can be obtained. When ηEx / ηEy exceeds 15, the stretch rate dependency becomes high, and in the production of a pressure-sensitive adhesive laminate by coextrusion molding, the balance of the moldability of each layer is easily disturbed by a slight change in conditions, and a good pressure-sensitive adhesive laminate is obtained. It's hard to be done. In addition, the measuring method of an extensional viscosity is based on the method shown in the Example mentioned later.

The pressure-sensitive adhesive laminate of the present invention comprises a polyolefin-based resin composition layer (A) and a pressure-sensitive adhesive layer (B) made of an acrylic pressure-sensitive adhesive composition, and is manufactured by coextrusion molding. From the viewpoint of adhesion between the polyolefin resin composition layer (A) and the adhesive layer (B), the polyolefin resin composition layer (A) is the polyolefin resin composition layer (A-1), the polyolefin resin composition. It is preferable that the layer (A-2) is provided, and the polyolefin resin composition layer (A-2) and the adhesive layer (B) are adjacent to each other. In particular, from the viewpoint of coextrusion processability, the polyolefin resin composition layer (A-1) as the first layer, the polyolefin resin composition layer (A-2) as the second layer, and the acrylic resin as the adhesive layer The structure of (A-1) / (A-2) / (B) which is the pressure-sensitive adhesive layer (B) made of the pressure-sensitive adhesive composition is more preferable.
Further, from the viewpoint of coextrusion processability, ηEa / ηEb of the polyolefin resin composition constituting the polyolefin resin composition layer (A-2) and an acrylic adhesive composition constituting the adhesive layer (B). The absolute value of the difference of ηEx / ηEy of the product is preferably 10 or less, and more preferably 7 or less.

  The 180 ° peel strength of the pressure-sensitive adhesive laminate of the present invention with respect to the acrylic resin plate at a peel rate of 300 mm / min is preferably 0.1 to 25 N / 25 mm, and more preferably 5 to 15 N / 25 mm. For example, when the pressure-sensitive adhesive laminate of the present invention is used as a protective film, if the peel strength is smaller than the above range, it may not be sufficiently attached to the adherend during the attaching operation, and peeling may occur. If the peeling strength is larger than the above range, the peeling operation becomes difficult and the adherend itself may be deformed.

  Examples of the method for producing the pressure-sensitive adhesive laminate of the present invention include a co-extrusion molding method using a feed block or a multi-manifold die, and further using a film forming apparatus such as a T-die extrusion molding machine or an inflation molding machine.

Although the thickness of the adhesion laminated body of this invention is not specifically limited, 0.01-2.0 mm is preferable, 0.02-0.5 mm is more preferable, 0.03-0.2 mm is further more preferable.
The pressure-sensitive adhesive laminate of the present invention is not particularly limited in the form of the previous stage applied to various uses, and examples thereof include a form superimposed on a sheet and a form wound in a roll. In a preferred embodiment of the pressure-sensitive adhesive laminate of the present invention, the polyolefin-based resin composition layer (A) includes a polyolefin-based resin composition (A-1) and a polyolefin-based resin composition layer (A-2). The layer structure with (B) is (A-1) / (A-2) / (B). With such a configuration, the outer layer of the polyolefin-based resin composition layer (A) corresponding to the base material is (A-1), and this has a small adhesive force with respect to the back surface with the adhesive layer (B). It can be made into the form wound up in roll shape. A roll shape is preferable from the viewpoint of improving productivity such as continuous bonding.

  The pressure-sensitive adhesive laminate of the present invention can be used for various applications. For example, for surface protection, masking, binding, packaging, office, label, decoration / display, bonding, dicing tape, sealing, anticorrosion / waterproof, medical / hygiene, glass scattering prevention , Adhesive tapes and films for electrical insulation, electronic device holding and fixing, semiconductor manufacturing, optical display films, adhesive optical films, electromagnetic wave shields, or sealing materials for electrical and electronic components. Specific examples are given below.

  Adhesive tape or film for surface protection can be used for various materials such as metal, plastic, rubber, and wood. Specifically, the surface of automobile members and optical members during paint processing, metal plastic processing and deep drawing processing Can be used for protection. Examples of the automobile member include a painted outer plate, a wheel, a mirror, a window, a light, and a light cover. Examples of the optical member include various image display devices such as a liquid crystal display, an organic EL display, a plasma display, and a field emission display; a polarizing film, a polarizing plate, a retardation plate, a light guide plate, a diffusion plate, an optical disc constituting film such as a DVD;・ Precise fine coated face plate for optical applications.

  Masking adhesive tapes and films can be used for masking when manufacturing printed circuit boards and flexible printed circuit boards; masking when plating and soldering with electronic equipment; manufacturing of vehicles such as automobiles, painting of vehicles and buildings, Examples include masking when printing, civil engineering and construction.

  Examples of binding applications include wire harnesses, electric wires, cables, fibers, pipes, coils, windings, steel materials, ducts, plastic bags, foods, vegetables, and grooms.

  Packaging applications include heavy goods packaging, export packaging, cardboard box sealing, can seals, and the like.

  Examples of office use include general office use, sealing, book repair, drawing, and memo.

  Examples of label usage include price, product display, tag, POP, sticker, stripe, name plate, decoration, and advertisement.

  The labels include paper, processed paper (paper subjected to aluminum vapor deposition, aluminum lamination, varnishing, resin processing, etc.), paper such as synthetic paper; cellophane, plastic material, cloth, wood and metal The label which uses a film etc. as a base material is mentioned. Specific examples of the substrate include, for example, high-quality paper, art paper, cast paper, thermal paper, foil paper; polyethylene terephthalate film, polyvinyl chloride film, OPP film, polylactic acid film, synthetic paper, synthetic paper thermal, overlamination A film etc. are mentioned.

  Examples of the adherend of the label include plastic products such as plastic bottles and foamed plastic cases; paper and cardboard products such as cardboard boxes; glass products such as glass bottles; metal products; and other inorganic material products such as ceramics. It is done.

  Examples of decoration / display applications include danger display stickers, line tapes, wiring markings, phosphorescent tapes, and reflective sheets.

  Examples of adhesive optical film applications include polarizing films, polarizing plates, retardation films, viewing angle widening films, brightness enhancement films, antireflection films, antiglare films, color filters, light guide plates, diffusion films, prism sheets, electromagnetic wave shielding films , Optical with adhesive layer formed on at least part or all of one or both sides of near infrared absorbing film, functional composite optical film, ITO bonding film, impact resistance imparting film, brightness enhancement film, visibility enhancement film, etc. A film etc. are mentioned. Such a pressure-sensitive adhesive optical film includes a film made of the pressure-sensitive adhesive laminate of the present invention as a protective film used for protecting the surface of the optical film. The adhesive optical film is suitably used for various image display devices such as liquid crystal display devices, PDPs, organic EL display devices, electronic paper, game machines, and mobile terminals.

  Examples of electrical insulation applications include protective coating or insulation of coils, interlayer insulation such as motors and transformers, and the like.

  Electronic device holding and fixing applications include carrier tape, packaging, CRT fixing, splicing, rib reinforcement, and the like.

  Examples of semiconductor manufacturing include protection of silicone wafers.

  Examples of bonding applications include various bonding fields, automobiles, trains, electrical equipment, printing plate fixing, construction, nameplate fixing, general household use, rough surfaces, uneven surfaces, and adhesion to curved surfaces.

  Sealing applications include heat insulation, vibration proofing, waterproofing, moisture proofing, soundproofing or dustproof sealing.

  Examples of anticorrosion / waterproofing include gas, water pipe corrosion prevention, large-diameter pipe corrosion prevention, and civil engineering building corrosion prevention.

  For medical and hygiene applications, analgesic / anti-inflammatory agents (plasters, papps), ischemic heart disease treatments, female hormone supplements, bronchodilators, cancer pain relieving agents, smoking cessation aids, cold patches, antipruritic patches, Percutaneous absorption medicine such as keratin softener; first aid adhesive bandage (with bactericidal agent), surgical dressing / surgical tape, adhesive bandage, hemostatic bond, human excrement treatment attachment tape (artificial anal fixation tape), suture tape, antibacterial tape Various tape applications such as fixed taping, self-adhesive bandage, oral mucosa adhesive tape, sports tape, hair removal tape; cosmetic use such as face pack, moisturizing sheet, exfoliating pack; cooling sheet, thermal warmer, dustproof, Waterproofing, pest capture, etc. are listed.

  Examples of electronic / electrical component sealing materials include liquid crystal monitors and solar cells.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention concretely, this invention is not limited to these Examples. Various physical properties in Examples and Comparative Examples were measured or evaluated by the following methods.

(1) Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the acrylic block copolymer (I)
The molecular weight was calculated as a standard polystyrene equivalent molecular weight by gel permeation chromatography (hereinafter abbreviated as GPC).
・ Device: GPC device “HLC-8020” manufactured by Tosoh Corporation
Separation column: “TSKgel GMHXL”, “G4000HXL” and “G5000HXL” manufactured by Tosoh Corporation are connected in series. Eluent: Tetrahydrofuran Eluent flow rate: 1.0 ml / min Column temperature: 40 ° C.
・ Detection method: Differential refractive index (RI)

(2) Content of each polymer block in the acrylic block copolymer (I)
^It calculated | required by < ¹ > H-NMR measurement.
・ Apparatus: JEOL nuclear magnetic resonance apparatus “JNM-ECX400”
・ Solvent: Deuterated chloroform
^{In the 1} H-NMR spectrum, signals near 3.6 ppm and 4.0 ppm are respectively represented by an ester group (—O—CH ₃ ) of a methyl methacrylate unit and an ester group (—O—C H ₂ ) of an acrylate unit. is attributed to -CH ₂ -CH ₂ -CH _3, or _{-O-C H 2 -CH (-CH} 2 -CH 3) -CH 2 -CH 2 -CH 2 -CH 3), co by the ratio of the integrated value The content of the polymerization component was determined.

(3) Melting point Using a differential scanning calorimeter (DSC) (manufactured by Mettler Toledo, TGA / DSC1 Star System), a sample melted by heating from 30 ° C. to 250 ° C. at a heating rate of 10 ° C./min. After cooling from 250 ° C. to 30 ° C. at a temperature decrease rate of 10 ° C./min, the peak top temperature of the endothermic peak measured when the temperature was increased from 30 ° C. to 250 ° C. again at a temperature increase rate of 10 ° C./min was taken as the melting point.

(4) Tensile modulus of polyolefin-based resin composition A polyolefin-based resin composition is molded into a sheet having a thickness of 1 mm at 200 ° C. by a press molding machine, and at a room temperature in accordance with the method described in ISO527-3, at a tensile rate. The measurement was performed under the condition of 300 mm / min.

(5) Melt flow rate of polyolefin resin composition Measured according to ISO 1133 under conditions of 190 ° C., 2.16 kg load and 10 minutes.

(6) Elongation viscosity characteristic (ηEa / ηEb) of polyolefin resin composition
A CEAST capillary rheometer “Rheological 5000” was extruded at a measurement capillary diameter of 0.5 mm and a resin temperature of 190 ° C., and an extension viscosity ηEa (Pa · s) at an extension speed of 10 (1 / s) and an extension speed of 1000 ( The elongational viscosity ηEb (Pa · s) at 1 / s) was measured and calculated.

(7) Elongation viscosity characteristic (ηEx / ηEy) of acrylic pressure-sensitive adhesive composition
A CEAST capillary rheometer “Rheological 5000” was extruded at a measurement capillary diameter of 0.5 mm and a resin temperature of 190 ° C., and an extension viscosity ηEx (Pa · s) at an extension speed of 10 (1 / s) and an extension speed of 1000 ( The elongational viscosity ηEy (Pa · s) at 1 / s) was measured and calculated.

(8) Coextrusion processability Using a three-layer, three-layer feed block type T-die coextrusion apparatus, the polyolefin resin composition and the acrylic pressure-sensitive adhesive composition are respectively fed to a T die, and the following coextrusion molding conditions Thus, the pressure-sensitive adhesive laminate of the present invention was produced.
Coextrusion molding conditions:
-Layer structure and thickness of each layer It shape | molded so that it might become polyolefin-type resin composition layer (A-1) / polyolefin-type resin composition layer (A-2) / adhesion layer (B) = 40micrometer / 10micrometer / 10micrometer.
-Extruder specifications and extrusion temperature A single screw extruder was used. The molding temperature in each extruder during extrusion of each layer is as follows: polyolefin resin composition layer (A-1): 200 ° C., polyolefin resin composition layer (A-2): 180 ° C., adhesive layer (B): 190 ° C
・ T-die, feed block, cooling roll specifications, molding temperature, take-up condition width T-die width is 300 mm, adapter (AD), T-die to the confluence of 3 types (2 types) of composition The temperature of the feed block for type 3 and 3 layers (molding device at the junction) was 200 ° C. The temperature of the cooling roll for picking up the pressure-sensitive adhesive laminate discharged from the T die was 40 ° C., and the pick-up speed was 4.0 m / min.
Surging of the resulting pressure-sensitive adhesive laminate (extruding amount is not constant in coextrusion molding, the shape and dimensions of the product are irregular or regularly fluctuate), appearance and take-up property during molding This was evaluated and used as an index for coextrusion processability.
(8) -1 Surging ○: Each layer is stable in the width direction and the entire flow direction, and the thickness is uniform. X: The flow at both ends or the central portion is excessive or insufficient, and the thickness is nonuniform (8)- 2 Surface smoothness Determined visually.
○: The surfaces of the polyolefin-based resin composition layer (A-1) and the pressure-sensitive adhesive layer (B) are smooth. X: The surfaces of the polyolefin-based resin composition layer (A-1) and the pressure-sensitive adhesive layer (B) are not smooth ( 8) -3 Take-up property ○: The thickness of the pressure-sensitive adhesive laminate does not change when it is taken up by a roll ×: The thickness of the pressure-sensitive adhesive laminate changes when it is taken up by a roll

(9) Peeling property of adhesive laminate The adhesive laminate produced by the method of (8) above is cut into a size of 50 mm x 50 mm, and the polyolefin resin composition layer (A) and the adhesive layer (B) are hand-held. Evaluation was made by peeling, and this was used as an index of delamination.
○: not peeled ×: peeled

(10) 180 ° peel strength of adhesive laminate to acrylic resin plate The adhesive laminate produced by the method of (8) above is cut into a width of 25 mm and a length of 100 mm, and attached to an acrylic resin (PMMA) plate. After being stored at room temperature (23 ° C) (unless otherwise specified, after 24 hours after bonding), in accordance with ISO 29862, peeled in the direction of 180 ° at a rate of 300 mm / min at 23 ° C. Measured.

[Raw resin used in Examples]
Below, the detail of raw material resin used by the Example and the comparative example is shown. Moreover, those physical property values are shown in Tables 1-3.

[Olefin polymer]
(1) “Prime Polypro J715M” (trade name, polypropylene resin manufactured by Prime Polymer Co., Ltd., melting point 160 ° C., tensile modulus 1300 MPa).
(2) “NOVATEC HF560” (trade name, polyethylene resin manufactured by Nippon Polyethylene Co., Ltd., melting point 134 ° C., tensile elastic modulus 1050 MPa).
(3) “Novatech LC600A” (trade name, polyethylene resin manufactured by Nippon Polyethylene Co., Ltd., melting point 106 ° C., tensile modulus 120 MPa)
(4) “Elvalloy AC12024S” (trade name, Mitsui DuPont Polychemical Co., Ltd. ethylene-methyl acrylate copolymer, methyl acrylate content in the copolymer: 24 mass%, 190 ° C., 2.16 kg load) Melt flow rate at 20 g / 10 min)
(5) “Nucleel N1525” (trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd., ethylene-methacrylic acid copolymer, methacrylic acid content in the copolymer: 15% by mass, 190 ° C., 2.16 kg (Melt flow rate under load: 25 g / 10 min)
(6) “Admer NF550” (trade name, manufactured by Mitsui Chemicals, maleic anhydride-modified polyethylene resin, maleic anhydride content in resin: 0.3 mass%, 190 ° C., melt flow rate at 2.16 kg load : 6.2g / 10min)
(7) “Elvalloy AC1218” (trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd., ethylene-methyl acrylate copolymer, methyl acrylate content in the copolymer: 18% by mass, 190 ° C., 2.16 kg) (Melt flow rate under load: 2 g / 10 min)

[Acrylic block copolymer (I)]
・ Acrylic block copolymer (I-1)
As shown in Table 3 below, methyl methacrylate polymer block (PMMA) -n-butyl acrylate polymer block (PnBA) -methyl methacrylate having a PMMA content of 20% by mass, Mw 81000, and molecular weight distribution 1.15 A triblock copolymer of combined blocks (PMMA) was used.

・ Acrylic block copolymer (I-2)
As shown in Table 3 below, the PMMA content is 20% by mass, the mass ratio of n-butyl acrylate / 2-ethylhexyl acrylate is 50/50, weight average molecular weight 80,000, molecular weight distribution (weight average molecular weight / number average). Molecular weight: 1.14 methyl methacrylate polymer block (PMMA) -n-butyl acrylate / 2-ethylhexyl acrylate polymer block (P (nBA / 2EHA))-methyl methacrylate polymer block (PMMA) ) Triblock copolymer was used.

[Examples 1-6, Comparative Examples 1-4]
Using the raw material resins described in Table 4, the pressure-sensitive adhesive laminate of the present invention was produced by the method (8). Test pieces were sampled from the obtained pressure-sensitive adhesive laminate and evaluated for coextrusion processability, delamination property, and 180 ° peel strength with respect to the acrylic resin plate. The results are shown in Table 4.

  The pressure-sensitive adhesive laminates obtained in Examples 1 to 5 are excellent in the balance of coextrusion processability, delamination property, and 180 ° peel strength with respect to the acrylic resin plate. On the other hand, the pressure-sensitive adhesive laminate of Comparative Example 1 had good coextrusion processability, but delamination occurred. In the pressure-sensitive adhesive laminate of Comparative Example 2, the polyolefin resin composition that is the raw material of the first layer is difficult to flow during coextrusion molding, and the resin does not spread uniformly to both ends with a T-die, and the thickness is non-uniform. became. When the pressure-sensitive adhesive laminate of Comparative Example 3 was coextruded and taken up by a roll, the thickness of each layer, particularly the thickness of the first layer, changed. In the pressure-sensitive adhesive laminate of Comparative Example 4, delamination between the pressure-sensitive adhesive layer (B) and the polyolefin resin composition layer occurred.

  The pressure-sensitive adhesive laminate of the present invention has good workability, excellent pressure-sensitive adhesive properties, is difficult to delaminate, has less sticking when formed into a roll, and is less expensive and environmentally friendly when a solution-type pressure-sensitive adhesive is used. Is produced by a coextrusion molding method. For this reason, it can be suitably used as a protective film, an adhesive tape, a label and the like used in the optical field, the automobile field, the electronics field, the medical field, the building field, the environmental field and the like.

Claims (15)

A polyolefin resin composition layer (A) and an adhesive layer (B) comprising an acrylic pressure-sensitive adhesive composition, wherein the acrylic pressure-sensitive adhesive composition comprises at least one polymer block comprising a methacrylic acid ester unit ( an acrylic block copolymer (I) having i-1) and at least one polymer block (i-2) comprising an acrylate unit,
The polyolefin resin composition layer (A) contains a polyolefin resin composition layer (A-1) having a tensile elastic modulus at 23 ° C. of 300 to 1800 MPa, and an olefin polymer containing a polar group. And a polyolefin resin composition layer (A-2) composed of a polyolefin resin composition having a melt flow rate of 5.0 to 50 g / 10 min measured at 190 ° C. and 2.16 kg. 2) A pressure -sensitive adhesive laminate that is a co-extrusion pressure-sensitive adhesive laminate in which the pressure-sensitive adhesive layer (B) is adjacent.   The acrylic pressure-sensitive adhesive composition constituting the adhesive layer (B) has an extensional viscosity ηEx (Pa · s) at an extension rate of 10 (1 / s) measured at 190 ° C. and an extension rate of 1000 (1 / The pressure-sensitive adhesive laminate according to claim 1, wherein the ratio (ηEx / ηEy) of the extensional viscosity ηEy (Pa · s) in s) is 15 or less.   Elongation viscosity ηEa (Pa · s) at an elongation rate of 10 (1 / s) measured at 190 ° C. and elongation measured at 190 ° C. of the polyolefin resin composition constituting the polyolefin resin composition layer (A-2) The pressure-sensitive adhesive laminate according to claim 1 or 2, wherein a ratio (ηEa / ηEb) of elongational viscosity ηEb (Pa · s) at a speed of 1000 (1 / s) is 15 or less.   The absolute value of the difference between ηEa / ηEb of the polyolefin resin composition constituting the polyolefin resin composition layer (A-2) and ηEx / ηEy of the acrylic adhesive composition constituting the adhesive layer (B) is The adhesion laminated body in any one of Claims 1-3 which is 10 or less.   The pressure-sensitive adhesive laminate according to any one of claims 1 to 4, wherein the content of the polymer block (i-1) in the acrylic block copolymer (I) is 5 to 50% by weight.   The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the acrylic block copolymer (I) is 1.0 to 2.0. The pressure-sensitive adhesive laminate described. The acrylic ester unit constituting the polymer block (i-2) of the acrylic block copolymer (I) has a general formula CH ₂ = CH-COOR ¹ (W) (wherein R ¹ has 4 carbon atoms). Represented by an acrylate ester (a) represented by ˜6 and a general formula CH ₂ ═CH—COOR ² (X) (wherein R ² represents an organic group having 7 to 12 carbon atoms) The acrylate ester (b) and the acrylate ester (a) and the acrylate ester (b) have a mass ratio (a) / (b) of 90/10 to 10/90. The pressure-sensitive adhesive laminate according to any one of 1 to 6.   The pressure-sensitive adhesive laminate according to claim 7, wherein the acrylic ester (a) is butyl acrylate.   The pressure-sensitive adhesive laminate according to claim 7 or 8, wherein the acrylic ester (b) is 2-ethylhexyl acrylate.   The pressure-sensitive adhesive laminate according to any one of claims 1 to 9, wherein the polyolefin-based resin composition layer (A-1) is composed of a polypropylene-based resin composition. The polyolefin resin composition layer (A-2) contains at least one resin selected from ethylene-acrylic acid ester copolymers, ethylene-methacrylic acid copolymers, and maleic anhydride-modified olefin resins. The adhesion laminated body in any one of Claims 1-10 comprised by these . Protective film made of an adhesive laminate according to any one of claims 1 to 11. Adhesive tape comprising a pressure-sensitive adhesive laminate according to any one of claims 1 to 11. Label comprising the pressure-sensitive laminate according to any one of claims 1 to 11. Melt flow measured at 190 ° C. and 2.16 kg, containing a polyolefin resin composition layer (A-1) having a tensile elastic modulus at 23 ° C. of 300 to 1800 MPa and an olefin polymer containing a polar group A polyolefin-based resin composition comprising a polyolefin-based resin composition layer (A-2) comprising a polyolefin-based resin composition having a rate of 5.0 to 50 g / 10 min and an adhesive layer (B) having a ηEx / ηEy of 15 or less. The pressure-sensitive adhesive laminate according to any one of claims 1 to 11 , wherein the physical layer (A-1), the polyolefin resin composition layer (A-2), and the pressure-sensitive adhesive layer (B) are coextruded. Production method.