JP2006282738A - Adhesive film or adhesive sheet, method for producing the same and adhesive product comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive film or adhesive sheet which has a proper adhesive force and produces little gel, to provide a method for producing the same, and to provide an adhesive product using the film or sheet as a substrate. <P>SOLUTION: This adhesive film or adhesive sheet comprises at least one adhesive layer comprising a resin composition containing at least one following component (A), and at least one layer comprising a thermoplastic resin. The method for producing the same, and the adhesive product comprising the same. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an adhesive film or an adhesive sheet, a method for producing the same, and an adhesive product comprising the same. More specifically, the present invention relates to a pressure-sensitive adhesive film or pressure-sensitive adhesive sheet having a suitable pressure-sensitive adhesive force and producing less gel, a method for producing the same, and a pressure-sensitive adhesive product based on the film or sheet.

  Adhesive film or adhesive sheet is a surface protective film for protecting the surface of products such as synthetic resin plates, decorative plywood, metal plates, and coated steel plates from dust adhesion, dirt, and scratches, and when baking and painting automobiles. It is used in various applications such as surface protective films when soldering printed circuit boards and solder. In recent years, a pressure-sensitive adhesive film or pressure-sensitive adhesive sheet in which a base material layer made of a polyolefin resin and a pressure-sensitive adhesive layer made of a low-density polyethylene or an ethylene-vinyl acetate copolymer are laminated by a coextrusion method that does not use an organic solvent at the time of manufacture. Has been developed. For example, in Patent Document 1, an adhesive layer made of polyethylene or ethylene-α-olefin copolymer having a density of 0.920 or less and a melt index of 1 to 20 is formed on one surface of a base material layer made of a thermoplastic resin. A surface protective film is described. Patent Document 2 describes a surface protective film having an adhesive layer made of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 18 to 25% on one surface of a base material layer made of high-density polyethylene. Yes.

JP-A-4-55488 JP-A-8-170056

However, the surface protective film in which the adhesive layer is made of polyethylene or ethylene-α-olefin copolymer has a problem that the adhesive force is insufficient depending on the application. In addition, the surface protective film having an adhesive layer made of an ethylene-vinyl acetate copolymer is excellent in adhesive force, but a gel is generated by receiving a thermal history inside the molding machine during the molding process. There is a problem that the appearance of the product is deteriorated by stopping the operation and replacing the screen pack, or in some cases, the gel is mixed into the adhesive film or the adhesive sheet.
Under such circumstances, the problem to be solved by the present invention, that is, the object of the present invention is to provide an adhesive film or adhesive sheet having an appropriate adhesive force and less gel formation, a method for producing the same, and the film or sheet. It is to provide an adhesive product as a material.

That is, the present invention is a pressure-sensitive adhesive film or pressure-sensitive adhesive sheet comprising at least one pressure-sensitive adhesive layer made of a resin composition containing at least one of the following components (A) and at least one base material layer made of a thermoplastic resin. The manufacturing method and an adhesive product comprising the same are provided.
Component (A): ethylene-acrylic acid ester copolymer or ethylene-methacrylic acid ester copolymer

  ADVANTAGE OF THE INVENTION According to this invention, the adhesive film or adhesive sheet which has moderate adhesive force and there is little production | generation of a gel, its manufacturing method, and the adhesive product which uses this film or sheet as a base material are provided.

  The component (A) used in the present invention is an ethylene-acrylic acid ester copolymer or an ethylene-methacrylic acid ester copolymer. Examples of the acrylate ester include ethyl acrylate, methyl acrylate, and propyl acrylate. Examples of the methacrylate ester include copolymers with methyl methacrylate, ethyl methacrylate, propyl methacrylate, and the like. It is done. Examples of the method for producing such a copolymer include a radical copolymerization reaction using a free radical generator such as an organic peroxide or oxygen. The radical copolymerization reaction is usually carried out at a polymerization temperature of 130 to 300 ° C., usually at a polymerization pressure of 49 to 294 MPa.

  The melt flow rate of the component (A) used in the present invention is preferably 1 g / 10 min or more from the viewpoint that the melt viscosity becomes high and an excessive load is not applied to the motor of the extruder, and the adhesive strength is obtained. Moreover, 20 g / 10 minutes or less is preferable from a viewpoint of suppressing generation | occurrence | production of extrusion surging or stabilizing a bubble in inflation molding. More preferably, it is 1-20 g / 10min, More preferably, it is 3-15g / 10min, Especially preferably, it is 5-10g / 10min.

  The durometer A hardness of the component (A) used in the present invention is preferably 55 or more from the viewpoint of easy feeding from the wound body of the pressure-sensitive adhesive film or pressure-sensitive adhesive sheet, and is preferably 98 or less from the viewpoint of obtaining adhesive force. More preferably, it is 60-96, More preferably, it is 80-94. The durometer A hardness is measured according to JIS-K-6253.

  The component (A) used in the present invention may be used by mixing an ethylene-acrylic acid ester copolymer and an ethylene-methacrylic acid ester copolymer in order to adjust the adhesive strength. Further, two or more types of copolymers having different acrylate contents in the ethylene-acrylic acid ester copolymer and different methacrylic acid ester contents in the ethylene-methacrylic acid ester copolymer may be used. Good.

In the present invention, the resin composition containing at least one component (A) preferably also contains the following component (B). The content of the component (B) is 99% by weight or less from the viewpoint of good drawability from the wound body, that is, the weight ratio of the components (A) and (B) is 99: 1 to 1: 99 is preferred.
Component (B): Amorphous α-olefin polymer (b1) satisfying all of the following requirements (b1) to (b4) (b1) No crystallization peak of 1 J / g or more is observed in the range of −100 to 200 ° C.
(B2) The content of the structural unit derived from the α-olefin is 30 mol% or more (provided that the entire polymer is 100 mol%).
(B3) The molecular weight distribution is 1 to 4.
(B4) The intrinsic viscosity is 0.1 to 10 dl / g.

  The weight ratio of components (A) and (B) is more preferably in the range of 95: 5 to 10:90, still more preferably in the range of 90:10 to 20:80, and particularly preferably 85:15 to 15. The range is 40:60, and most preferably the range is 80:20 to 60:40.

The component (B) used in the present invention is an amorphous α-olefin polymer that satisfies all the following requirements (b1) to (b4).
(B1) Neither a melting peak with a crystal melting calorie of 1 J / g or more and a crystallization peak with a crystallization calorie of 1 J / g or more by differential scanning calorimetry are observed in the range of −100 to 200 ° C.
(B2) The content of the structural unit derived from the α-olefin is 30 mol% or more (provided that the entire polymer is 100 mol%).
(B3) The molecular weight distribution is 1 to 4.
(B4) The intrinsic viscosity is 0.1 to 10 dl / g.

  As the component (B) used in the present invention, a melting peak with a crystal scanning calorific value of 1 J / g or more by differential scanning calorimetry or a crystallization peak with a crystallization calorie of 1 J / g or more is observed in the range of −100 to 200 ° C. When an amorphous α-olefin polymer is used, the adhesive strength of the resulting adhesive film or adhesive sheet may be reduced.

Component (B) used in the present invention has a content of structural units derived from α-olefin of 30 mol% or more, preferably 40 mol% or more, based on 100 mol% of the whole polymer. More preferably, it is 50 mol% or more. When there is too little this content, the adhesiveness of the adhesive film or adhesive sheet obtained may fall.
Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1- Tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nanodecene, 1-eicocene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl- 1-pentene, 2-ethyl-1-hexene, 2,2,4-trimethyl-1-pentene and the like are preferable, and propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1 -Decene, more preferably propylene, 1-butene and 1-hexene, and still more preferably propylene and 1-butene.

  The component (B) used in the present invention may contain a structural unit derived from a monomer other than an α-olefin within a range that satisfies other requirements (b1), (b3), and (b4). Examples of the monomer include ethylene, a polyene compound, a cyclic olefin, and a vinyl aromatic compound. The content of the structural unit is 70 mol% or less when the entire polymer is taken as 100 mol%.

  Examples of the polyene compound include conjugated polyene compounds and non-conjugated polyene compounds. Examples of the conjugated polyene compound include an aliphatic conjugated polyene compound and an alicyclic conjugated polyene compound, which have an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, and the like. Also good.

  Examples of the cyclic olefin include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene. 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1 , 2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano 1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8- Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5 8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro- 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro Phthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene, 5,6-dicarboxylnorbornene anhydrate, 5-dimethylaminonorbornene, 5-cyanonorbornene, cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, cyclohexene, 3-methylcyclohexene Xene, 4-methyl Examples include cyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene and the like.

  Examples of the vinyl aromatic compound include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, Examples include ethyl styrene and vinyl naphthalene.

  Examples of the component (B) used in the present invention include propylene homopolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene. -1-hexene copolymer, and the like, preferably a propylene homopolymer, a propylene-1-butene copolymer, and a propylene-ethylene-1-butene copolymer, more preferably propylene-1- It is a butene copolymer. The said polymer may be used by 1 type and may be used in combination of 2 or more type.

  The molecular weight distribution (Mw / Mn) of the component (B) used in the present invention is 1 to 4, preferably 1 to 3. Here, the molecular weight distribution (Mw / Mn) is measured by gel permeation chromatography (GPC). When the molecular weight distribution (Mw / Mn) is less than 1, the extrusion load may increase during the extrusion process of the adhesive film or the adhesive sheet. When the molecular weight distribution exceeds 4, the paste is removed when the adhesive film or the adhesive sheet is peeled off from the adherend. The rest may occur.

  The intrinsic viscosity [η] of the component (B) used in the present invention is 0.1 to 10 dl / g, preferably 0.5 to 10 dl / g, more preferably 0.5 to 10 dl / g. More preferably, it is 1-10 dl / g, Most preferably, it is 2-10 dl / g. When the intrinsic viscosity [η] is less than 0.1 dl / g, adhesive residue may be generated when the adhesive film or the adhesive sheet is peeled off from the adherend, and when it exceeds 10 dl / g, the adhesive film or the adhesive sheet. The extrusion load may increase during the extrusion process. The intrinsic viscosity [η] is measured in tetralin at 135 ° C.

The component (B) used in the present invention preferably has a dynamic loss elastic modulus of 1 × 10 ⁴ to 1 × 10 ⁷ Pa at 25 ° C. and 10 Hz measured with a dynamic viscoelasticity measuring apparatus. A more preferred range of the animal loss modulus is ^{1.5 × 10 4 Pa~9 × 10 6} Pa, more preferably from ^{2.0 × 10 4 Pa~8 × 10 6} Pa, particularly preferably Is 2.5 × 10 ⁴ Pa to 7 × 10 ⁶ Pa. When the dynamic loss elastic modulus is too small, the adhesive strength of the pressure-sensitive adhesive may be inferior, and when it is excessive, the adhesive strength of the pressure-sensitive adhesive at low temperatures may be inferior. The dynamic loss elastic modulus is measured by the following method. An amorphous α-olefin copolymer is molded into a test piece by molding it into a length of 40 mm, a width of 8 mm, and a thickness of 0.3 mm, using a viscoelastic spectrometer EXSTAR 5800 (manufactured by Seiko Instruments Inc.). Gripping length of 20 mm, initial elongation of 10 μm, displacement ± 10 μm, frequency of 10 Hz amplitude is given, the temperature is increased from −100 ° C. to 150 ° C. at a rate of 3 ° C./min, and the dynamic loss elastic modulus ( E ″) is measured, and E ″ at 25 ° C. and 10 Hz is obtained.

As a method for producing the component (B) used in the present invention, a known polymerization method using a known olefin polymerization catalyst is used. Among these, from the viewpoint of enhancing the flexibility and transparency of the resin composition, a polymerization method using a complex catalyst such as a metallocene complex or a nonmetallocene complex (for example, a slurry polymerization method, a solution polymerization method, Examples of the complex catalyst include, for example, JP 58-19309, JP 60-35005, JP 60-35006, JP JP-A-60-35007, JP-A-60-35008, JP-A-61-130314, JP-A-3-16388, JP-A-4-268307, JP-A-9-12790, Metallocene catalysts described in Kaihei 9-87313, JP-A-10-508055, JP-A-11-80233, JP 10-508055, and the like; No. 316710, JP-A-11-1000039, JP-A-11-80228, JP-A-11-80227, JP-T-10-513389, JP-A-10-338706, JP-A-11- Non-metallocene complex catalysts described in Japanese Patent No. 71420 can be given. Among these, metallocene catalysts are preferable from the viewpoint of availability, and examples of suitable metallocene catalysts include at least one cyclopentadiene-type anion skeleton and a periodic table group 3 having a C ₁ symmetric structure. To Group 12 transition metal complexes are preferred. Further, as a particularly preferred example of the production method using a metallocene catalyst, there can be mentioned the method described in EP-A-1211287.

  In the resin composition constituting the adhesive layer of the present invention, components other than the component (A) and the component (B) may be arbitrarily added in the range of 1 to 500 parts by weight with respect to the composition depending on the purpose. Is possible.

  The resin composition of the present invention is a rosin resin, a polyterpene resin, a synthetic petroleum resin, a coumarone resin, a phenol resin, a xylene resin, and a styrene resin as necessary, as long as the object of the present invention is not impaired. And other resins such as olefin polymers modified with isoprene-based resins, elastomers and low density polyethylene, unsaturated carboxylic acids or anhydrides thereof.

  Examples of the rosin resin include natural rosin, polymerized rosin, partially hydrogenated rosin, fully hydrogenated rosin, esterified products of these rosins (for example, glycerin ester, pentaerythritol ester, ethylene glycol ester and methyl ester) and rosin derivatives (for example, Disproportionated rosin, fumarized rosin and lime rosin).

  As the polyterpene resin, homopolymers of cyclic terpenes such as α-pinene, β-pinene and dipentene, copolymers of the cyclic terpenes, copolymers of the cyclic terpenes and phenolic compounds such as phenol and bisphenol. (For example, terpene-phenolic resins such as α-pinene-phenolic resin, dipentene-phenolic resin and terpene-bisphenolic resin) and aromatic modified terpene resins which are copolymers of the above cyclic terpenes and aromatic monomers. be able to.

As the synthetic petroleum resin, C ₅ fraction naphtha cracked oil, C ₆ -C ₁₁ fraction, other olefinic fractions homopolymers and copolymers, hydrogenated products of these homopolymers and copolymers Examples thereof include aliphatic petroleum resins, aromatic petroleum resins, alicyclic petroleum resins, and aliphatic-alicyclic copolymer resins. Examples of the synthetic petroleum resin further include a copolymer of the naphtha cracked oil and the terpene, and a copolymer petroleum resin that is a hydrogenated product of the copolymer.

Preferred C ₅ fractions of the naphtha cracked oil include isoprene, cyclopentadiene, 1,3-pentadiene, methylbutenes such as 2-methyl-1-butene and 2-methyl-2-butene, 1-pentene and 2-pentene. And pentenes as well as dicyclopentadiene. Preferred C ₆ -C ₁₁ fractions include methyl styrenes such as indene, styrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, α-methylstyrene and β-methylstyrene, methylindene, ethylindene, Mention may be made of vinyl xylene as well as propenylbenzene. Preferred other olefinic fractions include butene, hexene, heptene, octene, butadiene and octadiene.

  Examples of the phenolic resin include alkylphenol resins, alkylphenol-acetylene resins obtained by condensation of alkylphenol and acetylene, and modified products of these resins. Here, as these phenol resins, any of a novolak resin obtained by methylolation of phenol with an acid catalyst and a resol resin obtained by methylolation with an alkali catalyst may be used.

  Examples of the xylene-based resin include a xylene-formaldehyde resin composed of m-xylene and formaldehyde, and a modified resin obtained by adding a third component to the reaction.

  Examples of the styrenic resin include a low molecular weight product of styrene, a copolymer resin of α-methylstyrene and vinyltoluene, and a copolymer resin of styrene, acrylonitrile, and indene.

As the isoprene-based resin include a resin obtained by copolymerizing a C ₁₀ alicyclic compound and C ₁₀ chain compound is a dimer product of isoprene.

  Examples of the elastomer include natural rubber, polybutadiene, liquid polybutadiene, vinyl aromatic compound-conjugated diene copolymer (for example, styrene-butadiene random copolymer, styrene-isoprene random copolymer, styrene homopolymer block-butadiene homopolymer). Copolymer composed of polymer block, styrene homopolymer block-copolymer composed of isoprene homopolymer block, styrene homopolymer block-butadiene homopolymer block-styrene homopolymer block Copolymer, styrene homopolymer block-isoprene homopolymer block-copolymer composed of styrene homopolymer block, styrene homopolymer block-butadiene-isoprene copolymer block-styrene homopolymer block? Copolymer, styrene homopolymer block-styrene-butadiene copolymer block-copolymer composed of styrene homopolymer block), hydrogenated product of the vinyl aromatic compound-conjugated diene copolymer , Polyacrylonitrile rubber, acrylonitrile-butadiene copolymer rubber, partially hydrogenated acrylonitrile-butadiene copolymer rubber, butyl rubber, chloroprene rubber, fluorine rubber, chlorosulfonated polyethylene, silicon rubber, urethane rubber, isobutylene-isoprene copolymer rubber Further, halogenated isobutylene-isoprene copolymer rubber can be exemplified.

Examples of the low density polyethylene include an ethylene-α-olefin copolymer having a density of 910 kg / m ³ or less. Examples of the ethylene-α-olefin copolymer include “AFFINITY” manufactured by Dow Chemical Co., “Engage” manufactured by DuPont Dow Elastomer Co., “EXACT” manufactured by Exxon Chemical Co., “Tuffmer” manufactured by Mitsui Chemicals, and “Tuffmer” manufactured by Sumitomo Chemical Co., Ltd. Exelen FX ”,“ Exelen VL ”and the like.

  Examples of the olefin polymer modified with the unsaturated carboxylic acid or its anhydride include high density polyethylene, medium density polyethylene, low density polyethylene, ethylene and vinyl acetate, acrylic acid ester, butene, hexene, 4-methylpentene-1, and the like. Ethylene polymer, ionomer resin, propylene homopolymer, propylene copolymer copolymerized with α-olefins such as propylene and ethylene, butene, hexene, 4-methylpentene-1, polybutene- 1, poly-4-methylpentene-1, and a mixture of two or more selected from the above-mentioned olefin polymers, acrylic acid, methacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, vinyl benzoate An unsaturated carboxylic acid such as, an anhydride of the unsaturated carboxylic acid, or What graft-copolymerized ester of this unsaturated carboxylic acid is mentioned.

  The resin composition constituting the pressure-sensitive adhesive layer of the present invention includes an anti-aging agent, an antioxidant, an ozone degradation inhibitor, a stabilizer such as an ultraviolet absorber and a light stabilizer, an antistatic agent, a slip agent, if necessary. Additives such as internal release agents, colorants, dispersants, antiblocking agents, lubricants and antifogging agents, glass fibers, carbon fibers, metal fibers, glass beads, mica, calcium carbonate, potassium titanate whiskers, talc, aramid fibers Further, fillers such as barium sulfate, glass flakes and fluororesin, and mineral oil softeners such as naphthenic oil and paraffinic mineral oil may be used in combination.

  You may use the resin composition which comprises the adhesion layer of this invention in combination with a flame retardant as needed. Examples of flame retardants include antimony flame retardants, aluminum hydroxide, magnesium hydroxide, zinc borate, guanidine flame retardants, zirconium flame retardants, and other inorganic compounds, ammonium polyphosphate, ethylene bistris (2-cyanoethyl) phosphor Phosphoric esters and phosphorus compounds such as nium chloride, tris (tribromophenyl) phosphate, tris (tribromophenyl) phosphate and tris (3-hydroxypropyl) phosphine oxide, chlorinated paraffin, chlorinated polyolefin and perchlorocyclopentadecane Chlorinated flame retardants, as well as hexabromobenzene, ethylenebisdibromonorbornanedicarboximide, ethylenebistetrabromophthalimide, tetrabromobisphenol A derivatives, tetrabromobisphenol Nord S and tetrabromobisphenol dipentaerythritol brominated flame retardants, and the like. These flame retardants may be used alone or in combination of two or more.

  You may use the resin composition which comprises the adhesion layer of this invention in combination with a foaming agent as needed. As blowing agents, inorganic blowing agents such as sodium bicarbonate, ammonium bicarbonate and ammonium carbonate; nitroso compounds such as N, N′-dinitrosopentamethylenetetramine; azo compounds such as azocarbonamide and azoisobutyronitrile; and benzenesulfonyl Examples thereof include sulfonyl hydrazides such as hydrazine, p, p′-oxybis (benzenesulfonyl hydrazide), toluenesulfonyl hydrazide and toluenesulfonyl hydrazide derivatives. The foaming agent may be used in combination with foaming aids such as salicylic acid, urea and urea derivatives.

  The resin composition constituting the adhesive layer of the present invention may be used in combination with a high-frequency processing aid such as a polar polymer, if necessary. Examples of the high-frequency processing aid include a copolymer of ethylene and at least one comonomer. As comonomer, monocarboxylic acid such as acrylic acid, methacrylic acid, ethacrylic acid and crotonic acid, dicarboxylic acid such as maleic acid, fumaric acid, itaconic acid and citraconic acid, monoester of the above dicarboxylic acid, methacrylic acid ester such as methyl methacrylate And acrylic acid esters such as methyl acrylate and ethyl acrylate, vinyl esters of saturated carboxylic acids such as vinyl acetate and vinyl propionate, and ionomers of these acids and esters.

  You may use the resin composition which comprises the adhesion layer of this invention in combination with a tackifier as needed. As tackifiers, natural rosin resins such as rosin and dammar, modified rosin and its attractant, terpene resin and its modified body, aliphatic hydrocarbon resin, aromatic hydrocarbon resin, alkylphenol resin and coumarone indene Examples thereof include resins such as resins. Among these, terpenes such as terpene phenol and α-polyterpene are preferable. Terpenes include “YS Resin TO-105” and “Clearon” (trade names manufactured by Yasuhara Chemical Co., Ltd.), “Arcon”, “Esthegam” and “Pencel” (above, Arakawa Chemical Industries, Ltd.) Company name).

  The resin composition constituting the pressure-sensitive adhesive layer of the present invention is subjected to crosslinking such as sulfur crosslinking, peroxide crosslinking, metal ion crosslinking, silane crosslinking, resin crosslinking, electron beam crosslinking, etc., if necessary, by a known method. Can do. Examples of the crosslinking agent include sulfur, phenol resin, metal oxide, metal hydroxide, metal chloride, p-quinonedioxime, and bismaleimide. The crosslinking agent can be used in combination with a crosslinking accelerator in order to adjust the crosslinking rate. Examples of the crosslinking accelerator include oxidants such as red lead and dibenzothiazoyl sulfide. The crosslinking agent can be used in combination with a dispersing agent such as a metal oxide or stearic acid. Examples of the metal oxide include zinc oxide, magnesium oxide, lead oxide and calcium oxide. Among these, zinc oxide and magnesium oxide are preferable. The composition may be dynamically cross-linked in the presence of a cross-linking agent.

  As a method for producing the resin composition constituting the adhesive layer of the present invention, for example, a method of mixing the component (B) as it is with the component (A), or a component (B) and other polyolefin resin in advance. There is a method of preparing a master batch that is granulated and pelletized after melt-kneading and mixing the master batch with an olefin resin. In any method, mixing is performed by heat-melt kneading using a kneader or an extruder. Examples of the kneader include a kneader, a Banbury mixer, and a roll. Examples of the extruder include a single screw extruder and a twin screw extruder. Alternatively, resin pellets of component (A) and component (B) may be prepared and dry blended. Furthermore, the master batch may be powdered with at least one powder selected from calcium carbonate, barium sulfate, silica, talc, stearic acid, and olefin polymer powder, if necessary. These may be added during the production process of the masterbatch and previously kneaded in the pellets. The outer surface of the master batch pellet may be coated with silicone oil, silicone resin, or the like.

  Examples of the polyolefin resin include low-density polyethylene, medium-density polyethylene, ethylene-based polymers such as high-density polyethylene, homopolypropylene, propylene-based block copolymers, and propylene-based polymers such as propylene-α-olefin random copolymers, Examples include butene-1 polymer and 4-methyl-pentene-1 polymer.

  Examples of the method for producing the master batch include the method described in JP-A No. 2000-72923. In addition, the masterbatch is optionally subjected to a crosslinking treatment such as sulfur crosslinking, peroxide crosslinking, metal ion crosslinking, silane crosslinking, electron beam crosslinking, or decomposition such as peroxide decomposition by a conventionally known method. Processing may be performed.

  Examples of the thermoplastic resin constituting the base material layer of the present invention include polyolefin resin, polystyrene resin, polyester resin, polyamide resin, polyimide resin, acetate resin, polyethersulfone resin, polycarbonate resin, Examples include acrylic resins, silicone resins, thermoplastic urethane resins, and thermoplastic elastomers. One of these may be used, or two or more may be mixed or laminated.

The thermoplastic resin constituting the base material layer of the present invention is preferably a polyolefin resin because it can be recycled without being separated from the adhesive layer. Examples of polyolefin resins include ethylene polymers such as low density polyethylene, medium density polyethylene, and high density polyethylene, propylene polymers such as homopolypropylene, propylene block copolymers, and propylene-α-olefin random copolymers, butene. -1 polymer, 4-methyl-pentene-1 polymer, etc., among them, low density polyethylene is preferable from the viewpoint of flexibility.

  The thermoplastic resin constituting the base material layer of the present invention includes, as necessary, a crystal nucleating agent, a clarifying agent, a heat stabilizer, an ultraviolet stabilizer, an ultraviolet absorber, an ozone degradation inhibitor, a weather resistance stabilizer, Antifogging agent, rust preventive agent, ion trap agent, flame retardant, flame retardant aid, inorganic filler, antistatic agent, internal release agent, colorant, dispersant, antiblocking agent, lubricant, antibacterial agent, foaming agent, You may mix | blend various additives, such as a foaming adjuvant, a high frequency shaping | molding adjuvant, an organic pigment, and an inorganic pigment.

  The substrate layer may be a single layer or a multilayer composed of at least two layers. The surface of the base material layer may be treated by a known surface treatment method such as corona discharge treatment, plasma treatment, flame treatment, electron beam irradiation treatment, and ultraviolet irradiation treatment. The base material layer may be a colorless and transparent layer, or a colored or printed layer.

  In the pressure-sensitive adhesive film or pressure-sensitive adhesive sheet of the present invention, from the viewpoint of easy feeding of the pressure-sensitive adhesive film or pressure-sensitive adhesive sheet from the roll, that is, from the viewpoint of self-peeling property, a release paper is sandwiched in the scroll, or a release agent is placed on the back surface of the base material layer. It may be applied. Examples of release agents include silicone release agents and non-silicone release agents. Examples of the silicone release agent include a thermosetting silicone release agent, a photocurable silicone release agent, a copolymer release agent with another polymer, and a blend release agent with another polymer. Examples of the non-silicone release agent include a long-chain alkyl polymer, polyolefin, and a release agent mainly composed of a fluorine compound.

  In the present invention, the production method of the pressure-sensitive adhesive film or pressure-sensitive adhesive sheet is not particularly limited, but a known method such as a co-extrusion method such as a T-die molding method or an inflation molding method, a dry lamination method, an extrusion lamination method, etc. Is mentioned. The pressure-sensitive adhesive film of the present invention may be stretch-molded. Examples of the uniaxial stretching method include a commonly used roll stretching method. Examples of the biaxial stretching method include biaxial stretching after stretching uniaxially. Examples thereof include a sequential stretching method and a simultaneous biaxial stretching method such as a tubular stretching method.

  In this invention, the extrusion temperature at the time of manufacturing an adhesive film or an adhesive sheet is 100 to 350 degreeC normally, Preferably it is 130 to 300 degreeC, More preferably, it is 150 to 250 degreeC. When the temperature is lower than 100 ° C, the surface of the pressure-sensitive adhesive layer may be rough and the adhesive strength may be reduced. When the temperature is higher than 350 ° C, the melt viscosity may be too low to form the pressure-sensitive adhesive film.

  The layer structure of the pressure-sensitive adhesive film or pressure-sensitive adhesive sheet obtained in the present invention consists of at least two layers of a pressure-sensitive adhesive layer made of a resin composition and a base material layer made of a thermoplastic resin, and is usually about 2 to 7 layers. When the interfacial adhesive strength of the adhesive layer made of the resin composition and the base material layer made of the thermoplastic resin is weak, an adhesive resin layer such as a copolymer of ethylene and an unsaturated carboxylic acid anhydride is placed between them. Alternatively, in order to facilitate the feeding of the adhesive film from the roll of the adhesive film, a release layer such as a polyester resin, a polyamide resin, or a thermoplastic polyurethane is disposed adjacent to the adhesive layer or the base material layer. Also good.

Examples of the layer configuration of the pressure-sensitive adhesive film or pressure-sensitive adhesive sheet obtained in the present invention include pressure-sensitive adhesive layer / base material layer and pressure-sensitive adhesive layer / base material layer / pressure-sensitive adhesive layer.

  The total thickness of the pressure-sensitive adhesive film of the present invention is not particularly limited and can be arbitrarily selected. From the viewpoint of handling, it is preferably 1 to 500 μm, more preferably 10 to 300 μm, and still more preferably 20 to It is 100 micrometers, Most preferably, it is 30-80 micrometers.

  Although the total thickness of the adhesive sheet of this invention is not specifically limited, Although it can select arbitrarily, Preferably it is 500 micrometers-5 mm, More preferably, it is 1-3 mm.

  The thickness composition ratio of the pressure-sensitive adhesive film or pressure-sensitive adhesive sheet of the present invention is not particularly limited and can be arbitrarily selected. In order to obtain an appropriate adhesive strength, the thickness constitution ratio of the adhesive layer and the base material layer is preferably 1:99 to 99: 1, more preferably 5:95 to 80:20, 15 : It is more preferable that it is 85-60: 40, and it is especially preferable that it is 20: 80-40: 60.

  In the present invention, the pressure-sensitive adhesive product comprising the pressure-sensitive adhesive film or pressure-sensitive adhesive sheet includes all known pressure-sensitive adhesive products, such as a backgrinding tape for semiconductor wafers, a dicing tape, a protective tape for transporting electronic components, and a protective tape for printed circuit boards. Electronics field, window glass protection film, baking paint film, guard film for protecting automobiles to users, marking film for display, marking film for decoration, sponge tape for buffering, protection, heat insulation and soundproofing, etc. Automotive field, medical and hygiene materials field such as adhesive bandages and transdermal patches, and electrical insulation, identification, duct construction, window glass protection, curing, packaging, packaging, office use, home use Such as adhesive film and protective film for fixing, binding and repairing Mention may be made of the house and construction field.

  In the present invention, as an adhesive product comprising an adhesive film or an adhesive sheet, in particular, a synthetic resin plate, a stainless steel plate (for example, for building materials), an aluminum plate, a decorative plywood, a steel plate, a glass plate, a home appliance, a precision machine, and production To protect the surface of the car body during the time, to prevent damage when stacking, storing and transporting the goods, and when processing the goods (for example, bending or pressing) In order to prevent from being damaged, it can be preferably used.

  Hereinafter, the present invention will be described in more detail by way of examples.

[1] Physical property measurement method (1) Melt flow rate of component (A) (MFR, unit: g / 10 min)
The measurement was performed at a temperature of 190 ° C. and a load of 21.18 N according to the method defined in JIS K7210.

(2) Melting peak of component (B) According to JIS K7121, it measured by the differential scanning calorimeter (Seiko Electronics Co., Ltd. DSC220C: input compensation DSC). Specifically, as a condition adjustment, the sample polymer was heated from room temperature to 200 ° C. at 30 ° C./min and held at 200 ° C. for 5 minutes. Next, the temperature was lowered to −100 ° C. at 10 ° C./min, and the crystallization peak was measured. Subsequently, after hold | maintaining at -100 degreeC for 5 minute (s), it heated up at -10 degreeC / min from -100 degreeC to 200 degreeC, and measured the melting peak.

(3) Content of structural unit derived from each monomer contained in component (B) (unit: mol%)
It calculated based on the measurement result of a < ¹³ > C-NMR spectrum using the nuclear magnetic resonance apparatus (Bruker brand name AC-250). Specifically, the structure derived from propylene from the ratio of the spectral intensity of methyl carbon derived from structural units derived from propylene in the ¹³ C-NMR spectrum and the spectral intensity of methyl carbon derived from structural units derived from 1-butene. The composition ratio of the unit and the structural unit derived from 1-butene was calculated.

(4) Molecular weight distribution of component (B) (Mw / Mn)
It measured by the gel permeation chromatograph (GPC) method. Waters 150C / GPC is used as a measuring device, o-dichlorobenzene is used as a measuring solvent, Shodex Packed Column A-80M (2 pieces) manufactured by Showa Denko KK is used as a column, and a molecular weight standard substance is used. Is a standard polystyrene (manufactured by Tosoh Co., Ltd., molecular weight 68-8,400,000) under the conditions of an elution temperature of 140 ° C. and an elution solvent flow rate of 1.0 ml / min. 400 μl of a solution dissolved in dichlorobenzene is injected, and a polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) are measured with a differential refractometer, and a molecular weight distribution (Mw / Mn), which is a ratio of both, is obtained. Asked.

(5) Intrinsic viscosity of component (B) ([η], unit: dl / g)
Measurement was performed in a tetralin solvent at 135 ° C. using an Ubbelohde viscometer. A tetralin solution having an amorphous α-olefin copolymer concentration (c) of 0.6, 1.0, and 1.5 mg / ml is prepared, and the liquid level of the sample solution flows between the marked lines. The measurement time was measured three times. The measurement was repeated three times at each concentration. The average value of the three values obtained was defined as the specific viscosity (η _sp ) at that concentration, and the value obtained by extrapolating c of η _sp / c to zero was used as the intrinsic viscosity ([η ]).

(6) Adhesive strength (unit: cN / 25 mm width)
In a thermostatic chamber at 23 ° C., a strip-shaped test piece having a length of 150 mm and a width of 25 mm was collected from the adhesive film with the film forming direction as the longitudinal direction. A strip-shaped test piece is attached to an acrylic plate by pressure bonding with a rubber-coated roller having a mass of 2 kg, and this is left at 23 ° C. for 30 minutes. In an atmosphere of 23 ° C., the force required to peel the adhesive film from the acrylic plate under the conditions of a peeling angle of 90 degrees and a peeling speed of 200 mm / min was measured with an autograph AGS-500D manufactured by Shimadzu Corporation. Was the adhesive strength.

[2] Sample (A1): Aclift WH303 (ethylene-methyl methacrylate copolymer, MFR = 7 g / 10 min, durometer A hardness = 93) manufactured by Sumitomo Chemical Co., Ltd.
(A2): manufactured by Sumitomo Chemical Co., Ltd. ACRlift WH302 (ethylene-methyl methacrylate copolymer, MFR = 7 g / 10 min, durometer A hardness = 94)
(A3): Sumitomo Chemical Co., Ltd. Aclift WD301 (ethylene-methyl methacrylate copolymer, MFR = 7 g / 10 min, durometer A hardness = 96)
(A4): Sumitomo Chemical Co., Ltd. Aclift WH205 (ethylene-methyl methacrylate copolymer, MFR = 3 g / 10 min, durometer A hardness = 93)
(A5): manufactured by Sumitomo Chemical Co., Ltd. ACRlift WH206 (ethylene-methyl methacrylate copolymer, MFR = 2 g / 10 min, durometer A hardness = 93)
(C1): Sumikasen F235-P manufactured by Sumitomo Chemical Co., Ltd. (low density polyethylene, MFR = 2 g / 10 min, density = 924 kg / m ³ )
(C2): Sumikasen L705 manufactured by Sumitomo Chemical Co., Ltd. (low density polyethylene, MFR = 7 g / 10 min, density = 919 kg / m ³ )
(C3): Noblen FLX80E4 (homopolypropylene) manufactured by Sumitomo Chemical Co., Ltd.

[3] Examples 1 to 5
The adhesive layer resins described in Table 1 and Table 2 were supplied to the outer layer extruder of the Placo 3 layer blown film molding machine, and the base layer resin was supplied to the intermediate layer extruder and the inner layer extruder of the same machine. By molding at an extrusion temperature of 170 ° C., a blow ratio of 2.0, and a take-off speed of 15 m / min, an adhesive film having a thickness constitution ratio of 26:74 and a total thickness of 50 μm was produced. Various characteristic values of the obtained adhesive film are shown in Tables 1 and 2.

[4] Examples 6 to 10 and Comparative Example 1

(Example 6)
[Production of component (B)]
In a 100 L SUS reactor equipped with a stirrer, propylene and 1-butene were continuously polymerized by the following method using hydrogen as a molecular weight regulator to obtain an amorphous α-olefin copolymer. The corresponding propylene-1-butene copolymer was obtained.
From the lower part of the reactor, hexane as a polymerization solvent is continuously supplied at a supply rate of 100 L / hour, propylene is supplied at a supply rate of 24.00 kg / hour, and 1-butene is continuously supplied at a supply rate of 1.81 kg / hour. did.
Similarly, as a polymerization catalyst, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride is fed at a feed rate of 0.005 g / hour at triphenylmethyl. Tetrakis (pentafluorophenyl) borate was continuously fed at a feeding rate of 0.298 g / hour and triisobutylaluminum was continuously fed at a feeding rate of 2.315 g / hour.
The reaction solution was continuously extracted from the upper part of the reactor so that the volume of the reaction solution inside the reactor was always maintained at 100 L.
The polymerization reaction was carried out at 45 ° C. by circulating cooling water through a jacket attached to the outside of the reactor.
After a small amount of ethanol is added to the reaction liquid continuously extracted from the upper part of the reactor to stop the polymerization reaction, unreacted monomers are removed, and then the polymerization catalyst contained in the reaction liquid The residue was washed with water to remove the residue, and finally the polymerization solvent was removed with steam in a large amount of water to obtain a propylene-1-butene copolymer (hereinafter referred to as polymer B), which was 80. It dried under reduced pressure for 1 day at night. The content of structural units derived from propylene of the polymer B was 94.5 mol%, and the content of structural units derived from 1-butene was 5.5 mol%. In addition, [η] of the polymer B is 2.3 dl / g, the molecular weight distribution (Mw / Mn) is 2.2 (Mw = 420,000, Mn = 191000), and a melting peak and a crystallization peak are observed. There wasn't.

[Production of Masterbatch I of Component (B)]
85 parts by weight of amorphous propylene-1-butene copolymer produced by the above method, 15 parts by weight of crystalline ethylene-propylene copolymer (“Nobrene S131” manufactured by Sumitomo Chemical Co., Ltd.), hindered phenol type 0.2 parts by weight of antioxidant (“IRGANOX1010” manufactured by Ciba Specialty Chemicals Co., Ltd.) and 0.2 part of aromatic phosphite antioxidant (“IRGAFOS168” manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.2 After mixing parts by weight, 0.3 parts by weight of organic peroxide (“Perhexa 25B-8” manufactured by Nippon Oil & Fats Co., Ltd.) was blended with the obtained mixture (100.24 parts by weight), and biaxial A master batch I of an amorphous α-olefin copolymer was obtained by melt-kneading at 220 ° C. with an extruder.

  As an adhesive layer resin, a dry blend of 76.5% by weight of the component (A1) pellets and 23.5% by weight of the masterbatch I pellets of the above component (B) is a three-layer inflation film manufactured by Plako Co., Ltd. Supply to the outer layer extruder of the processing machine, and supply the component (C1) as the base layer resin to the intermediate layer extruder and the inner layer extruder of the same machine, extrusion temperature 170 ° C., blow ratio 2.0, take-up speed 15 m / By processing in minutes, an adhesive film having a thickness composition ratio of the adhesive layer and the base material layer of 26:74 and a total thickness of 50 μm was produced. Various characteristic values of the obtained adhesive film are shown in Table 2.

(Example 7)
The blend ratio of the pellet of the component (A1) and the pellet of the master batch of the amorphous α-olefin copolymer (B) is 70.6% by weight.
: An adhesive film was obtained in the same manner as in Example 6 except that the content was changed to 29.4% by weight. Various characteristic values of the obtained adhesive film are shown in Table 2.

(Example 8)
A pressure-sensitive adhesive film was obtained in the same manner as in Example 6 except that the blend ratio of the component (A1) pellets and the component (B) masterbatch pellets was 64.7% by weight: 35.3% by weight. Various characteristic values of the obtained adhesive film are shown in Table 2.

Example 9
[Production of Component (B) Masterbatch II]
Amorphous propylene-1-butene copolymer 40% by weight and component (A3) 60% by weight were melt-kneaded at 170 ° C. by a twin-screw extruder to produce an amorphous α-olefin copolymer. A combined masterbatch II was obtained.

  As the adhesive layer resin, the master batch II of the component (B) is supplied to the first layer extruder of the Tanabe Plastics Machinery Co., Ltd. 3-layer T die processing machine, and the component (C2) is used as the base layer resin. By supplying to the second layer extruder and the third layer extruder of the same machine and processing at an extrusion temperature of 250 ° C., a chill temperature of 30 ° C., and a take-off speed of 10 m / min, the thickness composition ratio of the adhesive layer and the base material layer is An adhesive film having a thickness of 17:83 and a total thickness of 60 μm was produced. Various characteristic values of the obtained adhesive film are shown in Table 2.

(Example 10)
An adhesive film was obtained in the same manner as in Example 9 except that the component (C3) was used as the base layer resin. Various characteristic values of the obtained adhesive film are shown in Table 2.

(Comparative Example 1)
An adhesive film was obtained in the same manner as in Example 6 except that the master batch of component (B) was used as the adhesive layer. However, the adhesive force could not be measured because it was impossible to feed the adhesive film from the roll.

It turns out that Examples 1-10 which satisfy the requirements of this invention are excellent in adhesive force and the draw-out property from a winding body. On the other hand, it can be seen that Comparative Example 1, which does not satisfy the requirements of the present invention, is poor in paying out from the wound body.

Claims (10)

A pressure-sensitive adhesive film or pressure-sensitive adhesive sheet comprising at least one pressure-sensitive adhesive layer made of a resin composition containing at least one of the following components (A) and at least one base material layer made of a thermoplastic resin.
Component (A): ethylene-acrylic acid ester copolymer or ethylene-methacrylic acid ester copolymer   The pressure-sensitive adhesive film or pressure-sensitive adhesive sheet according to claim 1, wherein the melt flow rate of the component (A) is 1 to 20 g / 10 minutes, and the durometer A hardness is 55 to 98. The pressure-sensitive adhesive film or pressure-sensitive adhesive sheet according to claim 1 or 2, wherein the resin composition further comprises the following component (B), and the weight ratio of the components (A) and (B) is 99: 1 to 1:99.
Component (B): Amorphous α-olefin polymer (b1) satisfying all of the following requirements (b1) to (b4) (b1) No crystallization peak of 1 J / g or more is observed in the range of −100 to 200 ° C.
(B2) The content of the structural unit derived from the α-olefin is 30 mol% or more (provided that the entire polymer is 100 mol%).
(B3) The molecular weight distribution is 1 to 4.
(B4) The intrinsic viscosity is 0.1 to 10 dl / g. The pressure-sensitive adhesive film or pressure-sensitive adhesive sheet according to claim 3, wherein the component (B) is an amorphous α-olefin polymer that further satisfies the following requirement (b5).
(B5) The dynamic loss elastic modulus at 25 ° C. and 10 Hz measured by a dynamic viscoelasticity measuring apparatus is 1 × 10 ⁴ to 1 × 10 ⁷ Pa.   The thermoplastic resin is a polyolefin resin, polystyrene resin, polyester resin, polyamide resin, polyimide resin, acetate resin, polyethersulfone resin, polycarbonate resin, acrylic resin, silicone resin, thermoplastic resin. The pressure-sensitive adhesive film or pressure-sensitive adhesive sheet according to any one of claims 1 to 4, which is at least one resin selected from the group consisting of a urethane resin and a thermoplastic elastomer.   The pressure-sensitive adhesive film or pressure-sensitive adhesive sheet according to claim 1, wherein the pressure-sensitive adhesive layer is disposed on both sides of the base material layer.   The pressure-sensitive adhesive film or pressure-sensitive adhesive sheet according to any one of claims 1 to 6, wherein the pressure-sensitive adhesive film or the pressure-sensitive adhesive sheet is produced at an extrusion temperature of 100 ° C to 350 ° C.   The pressure-sensitive adhesive film or pressure-sensitive adhesive sheet according to any one of claims 1 to 7, which is used for surface protection.   The manufacturing method of the adhesive film or adhesive sheet in any one of Claims 1-8. The adhesive product which consists of an adhesive film or an adhesive sheet in any one of Claims 1-9.