WO2006104133A1 - Composition de résine antistatique, composition de résine antistatique/autocollante, film autocollant et procédé servant à produire ceux-ci - Google Patents

Composition de résine antistatique, composition de résine antistatique/autocollante, film autocollant et procédé servant à produire ceux-ci Download PDF

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Publication number
WO2006104133A1
WO2006104133A1 PCT/JP2006/306254 JP2006306254W WO2006104133A1 WO 2006104133 A1 WO2006104133 A1 WO 2006104133A1 JP 2006306254 W JP2006306254 W JP 2006306254W WO 2006104133 A1 WO2006104133 A1 WO 2006104133A1
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Prior art keywords
component
antistatic
group
mass
polymer
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PCT/JP2006/306254
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English (en)
Japanese (ja)
Inventor
Masaaki Mawatari
Tetsuya Kubota
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Techno Polymer Co., Ltd.
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Application filed by Techno Polymer Co., Ltd. filed Critical Techno Polymer Co., Ltd.
Priority to KR1020077022040A priority Critical patent/KR101243090B1/ko
Priority to CN2006800144143A priority patent/CN101166784B/zh
Publication of WO2006104133A1 publication Critical patent/WO2006104133A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof

Definitions

  • Antistatic resin composition antistatic / adhesive resin composition, adhesive film, and method for producing the same
  • the present invention relates to an antistatic resin composition that gives a molded article such as a film or sheet having excellent antistatic properties.
  • Antistatic 'adhesive resin composition suitable for forming a highly antistatic adhesive layer on molded articles such as films and sheets, and an antistatic adhesive layer comprising the antistatic' adhesive resin composition The present invention relates to an adhesive film comprising: More specifically, the present invention is excellent in antistatic properties and transparency, antistatic resin composition excellent in surface appearance when formed into a film or the like, excellent in antistatic properties and adhesiveness, The present invention relates to an antistatic adhesive resin composition that allows easy control of adhesive strength, molded articles such as an adhesive film, a sheet, and a laminate using these compositions, and a method for producing the same.
  • Adhesive films in which an adhesive layer is disposed on a support are widely used in the fields of household appliances, construction materials, liquid crystal, and mobile phones. For example, partitions, windows, etc. It is used as a surface protective film for various articles.
  • the pressure-sensitive adhesive film usually has a pressure-sensitive adhesive layer formed on one side of the support, or a force that winds up in a tool-like form by providing a pressure-sensitive adhesive layer on one side of the support and a release layer on the other side. It is rolled up with a release paper attached to it. In the former case, the pressure-sensitive adhesive film is peeled from the release layer, and the pressure-sensitive adhesive layer is adhered to the adherend.
  • the release paper is removed and the adhesive layer is attached to the adherend during use.
  • the adhesive film is peeled off when the adherend is used, but static electricity is generated at this time (hereinafter referred to as peeling charge), and the film after peeling is removed.
  • peeling charge static electricity is generated at this time
  • dust was attached to the peeled film and it was easy to get dirty.
  • Such problems are caused by the pressure-sensitive adhesive layer and those caused by the support, both of which are desired to be solved.
  • the above problem is particularly a problem of peeling charging in the protective film on the polarizing plate surface of the liquid crystal display device.
  • LCDs have larger screens, higher definition, smaller frames, and thinner walls IC circuits are becoming narrower and their resistance to static electricity tends to be reduced, and peeling electrification causes a decrease in product yield.
  • Patent Document 1 discloses that a release layer is provided on one surface of a support having a polyethylene terephthalate (PET) film force, and an adhesive layer is provided on the other surface via an antistatic layer.
  • PET polyethylene terephthalate
  • Patent Document 2 discloses an adhesive film having an adhesive layer containing a charge control agent. Although the release charge generated in the adhesive layer can be eliminated to some extent, it is still static due to the support. There was a problem that occurred.
  • Patent Document 3 discloses a surface protective film having a polyolefin film as a support film and a styrene polymer block and a block copolymer having a conjugate power as a conjugation polymer block as an adhesive. Discloses a surface protective film using a polyolefin film as a support film and a block copolymer obtained by hydrogenating the conjugation polymer portion of the block copolymer as an adhesive.
  • these surface protective films which have been required in recent years as described above, do not satisfy the requirements for preventing anti-peeling, and Patent Document 5 also describes film strength such as polyolefin-based resin.
  • a surface protective film in which a binder layer is laminated on an antistatic layer laminated on one or both sides of a sheet-like substrate, and a pressure-sensitive adhesive layer is laminated on the binder layer.
  • this film has a problem that it is inferior in economic efficiency because an organic solvent is used when forming the antistatic layer, the process is complicated, and measures to prevent environmental pollution are necessary.
  • this film has another problem that even if an antistatic layer is provided in the middle, the antistatic effect is not sufficient, and in particular, the antistatic property on the sheet-like substrate side is not sufficient.
  • Patent Document 1 Japanese Patent Laid-Open No. 8-134416
  • Patent Document 2 JP 2004-155977 A
  • Patent Document 3 Japanese Patent Laid-Open No. 54-126243
  • Patent Document 4 Japanese Patent Laid-Open No. 61-103975
  • Patent Document 5 Japanese Unexamined Patent Publication No. 2000-328024 Disclosure of the invention
  • the adhesive film it is desired to improve the antistatic property for both the adhesive layer and the support.
  • any molded product must have at least a practically acceptable appearance.
  • An object of the present invention is to provide an antistatic resin composition which is excellent in antistatic properties and transparency and excellent in surface appearance when formed into a molded article such as a film.
  • Another object of the present invention is to provide an antistatic adhesive resin composition which is excellent in antistatic property and adhesiveness, easily controls adhesive force, and suitable for forming an adhesive layer.
  • Still another object of the present invention is to provide a support and an antistatic adhesive layer comprising the above antistatic adhesive resin composition, wherein the support and the adhesive layer are bonded with sufficient strength. It is in providing the adhesive film excellent in electroconductivity, and its manufacturing method, Preferably, it is providing the adhesive film excellent in transparency further, and its manufacturing method.
  • Still another object of the present invention is to provide various antistatic molded articles and antistatic laminates such as films and sheets, or to provide a support for the adhesive film. Furthermore, it is providing the antistatic resin composition excellent in heat resistance and the external appearance of a molded article.
  • compositions containing a predetermined amount of a polyolefin resin, a specific block copolymer, and a specific conjugation polymer have found that a composition containing a predetermined amount of a polyolefin resin, a specific block copolymer, and a specific conjugation polymer.
  • the present inventors have used a polyolefin resin containing a cyclic olefin component such as norbornene at a certain ratio as the polyolefin resin. It was found that a resin composition having excellent heat resistance while maintaining excellent antistatic properties can be obtained. A molded product with excellent antistatic properties can be obtained by molding this resin composition, and even when molded into a sheet or film and stacked on other molded products, the antistatic property is excellent. It has been found that a laminate can be provided.
  • the antistatic resin composition of the present invention can provide a molded product such as a film excellent in transparency and appearance as well as antistatic properties.
  • An antistatic adhesive resin composition is provided.
  • the antistatic adhesive resin composition of the present invention is not only antistatic but also excellent in transparency and appearance In addition to providing a molded product such as a film, it can be suitably used to form a transparent adhesive layer on a support having a polymer composition.
  • antistatic 'adhesive rosin composition of the present invention 0 to 40% by mass of the component (8), 6 to 25% by mass of the component (B), Antistatic adhesive composition containing 35 to 94% by mass of the above component (C) (provided that the total of the above component (A), component (B) and component (C) is 100% by mass). Is provided.
  • the antistatic adhesive resin composition according to the first preferred embodiment can be suitably used to obtain a transparent film by forming a transparent adhesive layer on a support film having polyolefin resin-repelling power.
  • the component (A) is modified with polyolefin ( ⁇ '-1) and ⁇ or a functional group.
  • Polyolefin ( ⁇ ′-2) wherein the component (C) is a hydrogenated product of a polymer mainly composed of conjugated genie compound units and aromatic beryl compound units, and the component ( ⁇ ) 0
  • An antistatic adhesive resin composition comprising: -59% by mass, the above component ( ⁇ ) 3-60% by mass, and the above component (C) 40-97% by mass is provided.
  • the component (C) is preferably hydrogenated.
  • the antistatic adhesive resin composition according to the second preferred embodiment forms a transparent film by forming a transparent adhesive layer on a support film made of various polymer compositions such as styrene resin. It can be used suitably to obtain.
  • Examples of preferable laminates according to the present invention include the following forms (1) to (4).
  • a support composed of a polyolefin resin composition, and an antistatic adhesive resin composition of the present invention, preferably disposed on at least one side of the support, preferably the first embodiment Anti-adhesive Finolem characterized by comprising an anti-static adhesive layer comprising an anti-static adhesive composition.
  • a support made of a thermoplastic polymer composition, and at least one surface side of the support, and the antistatic adhesive layer according to the first or second embodiment of the present invention An adhesive sheet or film-like laminate comprising an antistatic adhesive layer that also has a fat composition.
  • the sheet or film according to the above (1) to (4) is characterized by comprising a step of co-extruding the resin composition constituting the support and the antistatic adhesive resin composition of the present invention. It can be produced by a method for producing an adhesive sheet or film.
  • the above-mentioned component (A) is a polyolefin containing a cyclic olefin unit and having a glass transition temperature of 60 to 200 ° C.
  • the component (C) is composed of a polymer block (cl) mainly composed of a conjugated diene compound unit and an aromatic group. It is preferably at least one polymer selected from the group consisting of a block copolymer containing a polymer block (c2) mainly composed of vinyl compound units and a hydrogen additive thereof.
  • the antistatic resin composition and the antistatic adhesive resin composition of the present invention further comprise components (E1), (E2), (E2), Component (E3) and Component (E4) At least one antistatic agent (E) selected from the group consisting of a sufficient amount of the antistatic resin composition in an amount sufficient to improve the antistatic properties, Usually, it is preferable to contain 0.01-30 mass parts with respect to 100 mass parts in total of the said component (A), a component (B), and a component (C).
  • the antistatic resin composition of the present invention includes a predetermined amount of each of the specific components (A), (B) and (C), and thus has excellent antistatic properties and transparency. Outside the surface when molded products such as Excellent view.
  • the component (A) also has the above polyolefin resin (A-1) and (A-2) strength, a molded product having heat resistance can be obtained.
  • the antistatic adhesive composition of the present invention contains a specific amount of specific components (A), (B), and (C), the antistatic property, transparency, and adhesiveness are each included. Excellent adhesiveness and easy control of adhesive strength.
  • the antistatic adhesive composition of the present invention provides an antistatic adhesive layer having excellent adhesion to a support.
  • the adhesive film as a whole is excellent in antistatic properties and has a surface resistivity of 10 9 ⁇ or less under a predetermined condition. can do.
  • the pressure-sensitive adhesive film is excellent not only in antistatic properties but also in transparency, appearance, and adhesion between the support and the antistatic adhesive layer. According to the method for producing a pressure-sensitive adhesive film of the present invention, a pressure-sensitive adhesive film having excellent adhesion between the support and the antistatic pressure-sensitive adhesive layer can be easily formed.
  • (co) polymerization means homopolymerization and copolymerization
  • (meth) acryl means acryl and cocoon or methacryl
  • (Meth) atalylate means attalate and cocoon or metatalerate.
  • the antistatic resin composition of the present invention comprises (ii) polyolefin-based resin (also referred to as “component (ii)” in the present invention, except for the following (iii)): 30 to 95% by mass , ( ⁇ ) a block copolymer containing an olefin polymer block and a hydrophilic polymer block (also referred to as “component ( ⁇ )” in the present invention) 5 to 20% by mass, and (C) a conjugate At least one polymer selected from the group consisting of a polymer comprising a pheny compound unit and its hydrogenated product force (also referred to as “component (C)” in the present invention) is 0 to 50% by mass. (Provided that the total of component (A), component (B) and component (C) is 100% by mass).
  • the above component (A) is a polymer containing olefins having 2 or more carbon atoms as constituent monomer units. There is no particular limitation as long as it is an olefin-based resin and other than the component (B) described later.
  • a preferred component (A) is a (co) polymer containing olefins having 2 to 10 carbon atoms as constituent monomer units.
  • Preferred embodiments of the component (A) according to the present invention include: (1) a constituent monomer unit mainly composed of at least one selected from olefins having 2 or more carbon atoms (co) Polymer (hereinafter referred to as “polymer (1)”); (2) At least one selected from olefins having 2 or more carbon atoms, and a compound power capable of copolymerizing with the olefins At least one selected Examples include (co) polymer (2) (hereinafter referred to as “polymer (2)”) in which the constituent monomer units are mainly composed of species and force. These can be used alone or in combination of two or more.
  • polystyrene-based resin those obtained by a known polymerization method such as a high-pressure polymerization method, a low-pressure polymerization method, a metalocene catalyst method, and the like can be used.
  • acyclic olefins are typically used. Specific examples thereof include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene. 3-methyl-1-pentene, 4-methyl-1-pentene, 3-ethyl 1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl- Examples include 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and other a-olefins. These can be used alone or in combination of two or more. Of these, ethylene, propylene, 1-butene, 3-methyl-1-butene, and 4-methyl-1 pentene are preferable, and ethylene and propylene are
  • olefins As the olefins, cyclic olefins can also be used. Cyclic olefins are usually used in combination with the non-cyclic olefins.
  • cyclic olefin is not particularly limited as long as it is an alicyclic compound having one double bond, and examples thereof include compounds exemplified in JP-A-5-310845.
  • cyclic olefin is a compound having 11 or less carbon atoms.
  • norbornene having a carbon number of 11 or less is preferred. It is preferable that the enes (norbornene and Z or norbornene derivatives) occupy 50% by mass or more of the entire cyclic olefin.
  • norbornene include 2-norbornene (bicyclo [2.2.1] hept-2ene), 6-methylbicyclo [2.2.1] hept-2-ene, 6ethylbicyclo [2 2. 1] Hepto-2, 6- n-butylbicyclo [2.2.1] Hepto-2, 6 isobutylbicyclo [2.2.1] Hepto-2, 5, 6 dimethylbicyclo [ 2. 2.
  • cyclic olefins having 12 or more carbon atoms can be used alone or in combination with the above-mentioned compounds having 11 or less carbon atoms.
  • examples of the compound copolymerizable with the olefins in the polymer (2) include non-conjugated genie compounds.
  • examples of the non-conjugated genie compound include an acyclic geny compound and an alicyclic geny compound. These can be used alone or in combination of two or more.
  • Examples of acyclic gen compounds include straight chain acyclic gen compounds such as 1,4 monohexagen, 1,5 hexagen, 1,6-hexagen, 1,9-decadiene, etc .; 4-methyl-1,4 Kisagene, 5- Methinore 1,4 1-Hexagen, 7-Methinore 1,6-Octagen, 3,7 Dimethyl-1,6-Octagen, 5,7 Dimethylocta-1,6 Gen, 3,7 Dimethyl 1,7-Octagen 7 branched chain acyclic gen compounds such as methyl otater 1,6 gen and dihydromyrcene. These can be used alone or in combination of two or more.
  • the component (A) may be crystalline or amorphous, but preferably has a crystallinity of 20% or more by X-ray diffraction at room temperature. It is. In order to adjust the crystallinity, a known crystal nucleating agent may be added to the component (A).
  • the melting point (based on JIS K7121) of the component (A) is preferably 40 ° C or higher.
  • the molecular weight of the component (A) is not particularly limited, but from the viewpoint of moldability, melt flow rate (according to JIS K7210) ⁇ , preferably ⁇ 0.00-500g / 10 min, more preferably ⁇ . 01 ⁇ 500g / 10min, more preferably 0.05 ⁇ : LOOg / 10min, each value is preferred with a molecular weight corresponding to this value.
  • the polymer (1) includes polyethylene (high density polyethylene, low density polyethylene, linear polyethylene, meta-catalyzed polyethylene, etc.), ethylene copolymer (Copolymer containing 50% by mass or more of ethylene units based on all monomer units), ethylene 1-butene copolymer, polypropylene, propylene 'ethylene copolymer, propylene copolymer (propylene unit Copolymer containing 50% by mass or more based on the monomer unit), poly 1-butene, and the like.
  • polyethylene, polypropylene, and propylene / ethylene copolymers are preferred.
  • the propylene / ethylene copolymer a force random copolymer having a random copolymer, a block copolymer and the like is particularly preferable. These can be used alone or in combination of two or more.
  • the melting point (in accordance with JIS K7121) of the above polyethylene or ethylene copolymer (ethylene 'a-olefin copolymer, etc.) is preferably 40 ° C or higher, and the molecular weight is not particularly limited. Therefore, the melt flow rate (conforming to JIS K6922) is preferably 0.001 to 500 gZlO, more preferably 0.01 to LOOgZlO, and preferably has a molecular weight corresponding to each value.
  • the melting point of the above-mentioned polypropylene or propylene copolymer is preferably 40 ° C or higher, and the molecular weight is not particularly limited, but from the viewpoint of moldability.
  • the melt flow rate (conforming to JIS K7210) is preferably 0.01 to 500 gZl0 minutes, more preferably 0.05 to LOOgZlO, each value Those having a molecular weight corresponding to are preferred.
  • the polymer (2) includes an ethylene'norbornene copolymer, a propylene-norbornene copolymer, an ethylene'propylene-5 ethylidene 2-norbornene copolymer, and the like. Can be mentioned. These can be used alone or in combination of two or more. These polymers are preferably those produced by the metamouth catalyst method. In addition, each content of the monomer unit which comprises said copolymer is not specifically limited.
  • the component (A) contains a cyclic olefin unit as a constituent monomer unit and has a glass transition temperature of 60 to 200 ° C. It is preferable to use both the polyolefin-based resin (A-1) and the polyolefin-based resin (A-2) containing no cyclic olefin units.
  • the polyolefin resin (A-1) and (A-2) are also referred to as the component (A-1) and the component (A-2), respectively.
  • the glass transition temperature of the polyolefin resin (A-1) is preferably 60 to 200 ° C, more preferably 70 to 200 ° C, still more preferably 70 to 190 ° C, and particularly preferably 75. ⁇ 185 ° C. If this glass transition temperature is too low, the effect of imparting heat resistance is not sufficient, while if it is too high, the surface appearance of the molded product may deteriorate. In order to obtain a polymer having the above glass transition temperature, it is preferable that the cyclic olefin is copolymerized in the range of 40 to 90% by mass with respect to the whole component (A-1).
  • the glass transition temperature can be measured by a known method such as using a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the melt flow rate (measured at a temperature of 260 ° C. and a load of 2.16 kg according to ISO 1133) of this polyolefin resin (A-1) is preferably from 0.1 to LOOmlZlO. Furthermore, it is preferable that this polyolefin resin (A-1) is amorphous.
  • the polyolefin resin (A-2) used in combination with the polyolefin resin (A-1) use all the components (A) that do not contain a cyclic olefin unit as a constituent monomer unit. The description of the component (A) can be applied to the polyolefin resin (A-2) as it is.
  • the mixing ratio of the polyolefin-based resin (A-1) and the polyolefin-based resin (A-2) is When the total of these is 100% by mass, the component (A-1) is 1 to 95% by mass and the component (A-2) is 99 to 5% by mass, preferably the component (A-1) is 10 to 90%.
  • the content of component (A) is 30 to 30% when the sum of component (A), component (B) and component (C) is 100% by mass. It is 95% by mass, preferably 42 to 92% by mass, more preferably 49 to 92% by mass, and particularly preferably 49 to 90% by mass. If this content is less than 30% by mass, the rigidity tends to decrease, while if it exceeds 95% by mass, the antistatic property tends to be inferior.
  • Component (B) according to the present invention comprises an olefin polymer block (also referred to as “polymer block (bl)” in the present invention) and a hydrophilic polymer block (in the present invention, “polymer block”). (b2) ”))).
  • This component (B) can impart antistatic properties to the antistatic resin composition of the present invention.
  • this component (B) can be used alone or in combination of two or more.
  • the arrangement of the polymer blocks (bl) and (b2) is not particularly limited, and may have a block structure exemplified in the following (1) to (5). it can.
  • ml is an integer of 1 or more
  • m2 and m2 ′ are both integers of 2 or more, and may be the same or different.
  • each structure when there are a plurality of polymer blocks (bl) and (b2), each block may be the same as or different from each other.
  • block structures (1), (2) and (3) that is, polymer blocks (bl) and (b 2) It is preferable to arrange alternately repeatedly.
  • the component (B) is a force component (B) mainly composed of the above-mentioned block copolymer, and other (co) blocks such as a polyamide block and a polyester block in a proportion of 20% by mass or less. Polymer blocks can also be included.
  • the bond form of the polymer blocks (bl) and (b2) is preferably an ester bond, an amide bond, an ether bond, a urethane bond or an imide bond.
  • the polymer block (bl) is a block having a polymer strength mainly composed of olefin units, and examples of the compound forming the polymer include acyclic olefins having 2 or more carbon atoms and cyclic olefins. It is done.
  • Examples of acyclic olefins include ethylene and propylene, 1-butene, 1 pentene, 1-hexene, 3-methyl 1-butene, 4-methyl 1-pentene, 3-methylhexene 1
  • Examples include olefin.
  • An example of cyclic olefin is norbornene. These compounds can be used alone or in combination of two or more.
  • the polymer block (bl) includes 4-methyl-1,4 monohexagen, 5-methinoleyl 1,4 monohexagen, 7-methylenole 1,6-octagen, 1,9-decadene. It may be a polymer containing non-conjugated gen as a constituent monomer unit.
  • both ends of the molecule of the polymer block (bl) are A carboxyl group, a hydroxyl group, an amino group, an acid anhydride group, an oxazoline group, and an epoxy group.
  • Examples of a method for imparting these functional groups include a method of subjecting a polymer having a double bond at the molecular end obtained by a thermal degradation method to an addition reaction of an unsaturated compound having the above functional group.
  • the number average molecular weight of the above polymer block (bl) in terms of polystyrene by gel permeation chromatography (GPC) is preferably ⁇ 800 to 20,000, more preferably ⁇ 100 to : L0, 000, more preferred ⁇ is 1,200 to 6,000.
  • the polymer block (bl) may be contained alone or in combination of two or more in the component (B).
  • the polymer block (b2) is a polymer-strength block having a hydrophilic group such as a hydroxyl group, an amino group, or an ether group, and preferably has a polymer force having an ether bond in the main chain. is there.
  • the polymer include polyether (b2-a), polyether-containing hydrophilic polymer (b2-b), and eron polymer (b2-c).
  • polyether (b2-a) examples include polyether diol, polyether diamine, and modified products thereof.
  • polyether-containing hydrophilic polymer (b2-b) examples include polyether ester amide having a polyether diol segment, polyether amide imide having a polyether diol segment, polyether ester having a polyether diol segment, Polyether amides having a segment of ether diamine and polyether urethanes having a segment of polyether diol or polyether diamine.
  • the er-on polymer (b2-c) has a dicarboxylic acid having a sulfo group and a polyether (b2-a) as essential constituent units, and preferably 2 to 80 units in one molecule.
  • Preferable examples are eron polymers having 3 to 60 sulfo groups.
  • polymer block (b2) may be composed of only one type of block, or may contain two or more types of blocks.
  • a preferred component (b2) is a polyether (b2-a), more preferably a polyether diol and a polyetheramine, and particularly preferably a polyetherdiol.
  • polyether diol in the polyether (b2-a) is represented by the general formula (1):
  • Examples include those represented by ⁇ .
  • E 1 is a divalent hydroxyl group-containing compound, and the residue is a residue excluding the hydroxyl group
  • a 1 is an alkylene group having 2 to 4 carbon atoms
  • n and are integers of usually 1 to 300, preferably 2 to 250, particularly preferably 10 to 100.
  • N may be the same or different.
  • Examples of the divalent hydroxyl group-containing compound include a compound containing two alcoholic or phenolic hydroxyl groups in one molecule, that is, a dihydroxy compound. Specifically, Examples include dihydric alcohols, dihydric phenols, and diols containing tertiary amino groups. These can be used alone or in combination of two or more.
  • the dihydric alcohol is preferably a compound having 2 to 12 carbon atoms which may be aliphatic, alicyclic or aromatic.
  • aliphatic dihydric alcohol examples include ethylene glycol, alkylene glycol such as propylene glycol such as 1,3 propylene glycol, 1,4 butanediol, 1,6-hexanediol, 1,9-nonanediol, and neopentyl glycol. 1, 12-dodecanediol and the like.
  • alicyclic dihydric alcohols examples include 1,2- and 1,3-cyclopentanediol, 1,2-, 1,3 and 1,4-cyclohexanediol, and 1,4-cyclohexane. Examples include dimethanol.
  • aromatic dihydric alcohol examples include xylene diol.
  • the divalent phenol is preferably a compound having 6 to 18 carbon atoms such as monocyclic divalent phenol, bisphenol, condensed polycyclic divalent phenol and the like.
  • Examples of the monocyclic divalent phenol include hydroquinone, catechol, resorcin, and urushiol.
  • bisphenol examples include bisphenol A, bisphenol F, bisphenol S, 4,4′-dihydroxydiphenyl-1,2-butane, dihydroxybiphenyl, dihydroxydiphenyl ether, and the like.
  • Examples of the condensed polycyclic divalent phenol include dihydroxynaphthalene and binaphthol.
  • examples of the tertiary amino group-containing diol include N alkyl dialkylanolamines having 1 to 8 carbon atoms.
  • E 2 represents a hydroxyl group from the divalent hydroxyl group-containing compound described in the general formula (1).
  • the residue A 2 except at least part of the general formula (3) —CHR—CHR ′ (wherein one of RR ′ is represented by the general formula (4) CH 0 (A 3 0) R And the other is H.
  • X is 1 10 integer
  • R represents H or C 1 10 alkyl group, group, an alkyl ⁇ aryl group, ⁇ reel alkyl or Ashiru group, A 3 4 2 carbon atoms
  • the remaining alkylene group may be a C 24 alkyl group.
  • the m (OA 2 ) and the (A 2 0) may be the same or different.
  • M may be the same as or different from m.
  • the polyether diol represented by the general formula (1) can be produced by addition reaction of an alkylene oxide to a divalent hydroxyl group-containing compound.
  • alkylene oxide examples include alkylene oxides having 24 carbon atoms, such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,4-butylene oxide, 2,3-butylene oxide, 1,3-butylene oxide, and these Two or more combined systems are used.
  • the bond type may be random and ⁇ or block or misaligned.
  • Preferred as alkylene oxides are block and soot or random addition with ethylene oxide alone and in combination with ethylene oxide and other alkylene oxides.
  • the number of alkylene oxides added is preferably an integer of 1300, more preferably 2250, and particularly preferably 10 to L00 per hydroxyl group of the divalent hydroxyl group-containing compound.
  • Preferable methods for producing the polyether diol represented by the general formula (2) include the following methods (1) and (II).
  • a 4 is an alkylene group having 24 carbon atoms, p is an integer of 1 10, R 1 is H or an alkyl group having 1 10 carbon atoms, an aryl group, an alkyl aryl group, an aryl alkyl group. Group or acyl group.
  • alkylene oxide having 2 to 4 carbon atoms used here all of those described above can be used.
  • the polyether diamine the polymer represented by the general formula (1) can be used in which a hydroxyl group is substituted with an amino group by a known method.
  • the polyether amide is composed of polyamide and polyether diamine.
  • the polyether amide imide is composed of a polyamide imide having at least one imide ring and a polyether diol.
  • the polyether ester is composed of polyester and polyether diol.
  • the polyether ester amide is composed of a polyamide having a carboxyl group at the terminal and a polyether diol.
  • the polyether urethane is composed of an organic diisocyanate and a polyether diol, or is composed of an organic diisocyanate, a polyether diamine, and a chain extender.
  • the arion polymer (b2-c) can be obtained by modifying the polymer block, and has, for example, a block composed of polyether diol and Z or polyether diamine and a sulfonyl group. It is preferable to copolymerize with dicarboxylic acid units. Can yield a polymer having 2 to 80, more preferably 3 to 60, sulfo groups.
  • the component contains at least one salt (H) selected from the group consisting of alkali metals and alkaline earth metals.
  • H salt
  • these components can be contained before polymerization of component (B), during polymerization of component (B), or after polymerization of component (B).
  • it can be blended when the antistatic resin composition of the present invention is produced, or can be contained by a method combining these.
  • Component (H) includes organic acids such as alkali metals such as lithium, sodium and potassium, and alkaline earth metals such as Z, magnesium and calcium, sulfonic acids, salts of inorganic acids, and halides.
  • organic acids such as alkali metals such as lithium, sodium and potassium, and alkaline earth metals such as Z, magnesium and calcium, sulfonic acids, salts of inorganic acids, and halides.
  • component (H) include lithium chloride, sodium chloride, potassium salt, alkali metal halides such as lithium bromide, sodium bromide, potassium bromide; Inorganic acid salts of alkali metals such as lithium borate, sodium perchlorate and potassium perchlorate; organic acid salts of alkali metals such as potassium acetate and lithium stearate; octyl sulfonic acid, dodecyl sulfonic acid, tetradecyl sulfonic acid, stearyl Alkali metal salts of alkyl sulfonic acids having 8 to 24 carbon atoms in the alkyl group, such as sulfonic acid, tetracosyl sulfonic acid and 2-ethylhexyl sulfonic acid; aromatic sulfonic acids such as phenyl sulfonic acid and naphthyl sulfonic acid Alkali metal salts; oct
  • the polymer blocks (bl) and (b2) have the above block structure.
  • the structures (1) to (5) are preferably constituted by the arrangements shown in the block structures (1) to (3).
  • composition ratio (bl) / (b2) of the polymer blocks (bl) and (b2) is preferably 10 to 90% by mass, ZlO to 90% by mass, more preferably when the total of these is 100% by mass Is 20 to 80 mass% Z20 to 80 mass%, more preferably 30 to 70 mass% Z30 to 70 mass%.
  • the average repeat number of the polymer blocks (b 1) and (b2) is preferably 2 to 50.
  • the component (B) can be obtained by polymerizing the olefin polymer block (bl) and the hydrophilic polymer block (b2) by a known method.
  • it can be produced by polymerizing the polymer block (bl) and the polymer block (b2) at 200 to 250 ° C. under reduced pressure.
  • a known polymerization catalyst can be used in the polymerization reaction.
  • Tin-based catalysts such as monobutyltin oxide, antimony-based catalysts such as antimony trioxide and antimony dioxide, tetrabutyl titanate, and the like Titanium-based catalyst, zirconium hydroxide, zirconium-based catalyst such as zirconium oxide, zirconium acetate, and the like, Group organic acid salt Catalytic power One or a combination of two or more selected.
  • the component (B) can be produced, for example, by the method described in JP-A-2001-278985, JP-A-2003-48990, and the like.
  • the content of component (B) is 5 to 5 when the total of component (A), component (B) and component (C) is 100% by mass. It is 20% by mass, preferably 8 to 18% by mass, more preferably 8 to 16% by mass, and particularly preferably 10 to 16% by mass. If the content is less than 5% by mass, the antistatic property tends to be inferior, whereas if it exceeds 20% by mass, the surface appearance of the molded product tends to be inferior.
  • Component (C) according to the present invention is a polymer containing a conjugated pheny compound unit (also referred to as “union (Cl)”. And a hydrogenated product of the polymer (CI) (also referred to as “polymer (C2)” in the present invention).
  • the polymer (C1) may be a polymer containing only a conjugated diene compound unit, or a polymer containing the conjugated diene compound unit and an aromatic vinyl compound unit.
  • Conjugated Genie compounds constituting the conjugated Genie compound unit include 1,3-butadiene, isoprene, hexagen, 2,3-dimethyl-1,3-butadiene, 1,3-penta. Gen etc. are mentioned. These can be used alone or in combination of two or more. Of these, 1,3-butadiene and isoprene are preferred. Therefore, examples of the polymer (C1) containing only the above conjugated diene compound unit include polybutadiene and polyisoprene.
  • examples of the aromatic vinyl compound constituting the aromatic vinyl compound unit include styrene, (X-methylstyrene, hydroxystyrene, etc. These may be used alone. Alternatively, two or more types can be used in combination, and among these, styrene is preferred, with styrene and ⁇ -methylstyrene being preferred.
  • each compound may be contained singly or in combination of two or more.
  • the content of the conjugated conjugated compound unit in the polymer (C1) is preferably 30 to 95 when the total of the conjugated genic compound unit and the aromatic conjugated compound unit is 100% by mass. mass 0/0, more preferably 50 to 95 weight 0/0, particularly preferably Ru 60 to 93% by mass.
  • the content of the aromatic vinyl compound unit in the polymer (C1) is preferably when the total of the synergistic pheny compound unit and the aromatic vinyl compound unit is 100% by mass. Is 5 to 70% by mass, more preferably 5 to 50% by mass, and particularly preferably 7 to 40% by mass.
  • the total amount of the conjugated conjugated compound unit and the aromatic vinyl compound compound unit is preferably 80% by mass or more, more preferably 90%, based on all monomer units constituting the polymer (C1). It is at least mass%.
  • the polymer (C1) includes a conjugation compound unit and an aromatic bur compound unit
  • the polymer (C1) is copolymerized with the aromatic bur compound and the conjugated gen compound. It may further comprise other units that also provide possible compound power. In addition, this unit may be included alone or in combination of two or more.
  • the polymer (C1) may be a block copolymer, a random copolymer, or a bond in which a random copolymer and a block copolymer are mixed. It may be in a form. These can be used alone or in combination of two or more. Of these, block copolymers are preferred.
  • the polymer (C1) includes a conjugated gen compound unit and an aromatic bur compound unit
  • the conjugated gen compound unit mainly (preferably 80% by mass with respect to all monomer units). Or more, more preferably 90% by mass or more, more preferably 99% by mass or more) from the polymer block (cl) and the aromatic vinyl compound compound unit (preferably 80% by mass with respect to all monomer units).
  • a block copolymer containing the above polymer block (c2) is preferred.
  • the polymer block (cl) and the polymer block (c2) may include the aromatic beryl compound unit and the conjugated Jen compound unit, respectively.
  • the polymer block (cl) usually has a vinyl bond, and its content (total) is not particularly limited. That is, it may be 50% or more, or less than 50%. In the former case, it is usually 50 to 95% with respect to the polymer block (cl). In the latter case, it becomes easy to adjust the rigidity and transparency of the molded product.
  • polymer block (c2) force conjugation compound unit In the case where the polymer block (c2) force conjugation compound unit is included, it may have a bull bond.
  • the polymer block (cl) is a block in which the polymer block (cl) is bonded in any form of a random shape, a block shape, and a tapered block shape, particularly when two or more kinds of conjugated genie compound units are included. May be.
  • this polymer block (cl) is a polymer block having a different bull bond content derived from a conjugation compound unit which may contain 1 to 10 taper blocks in which aromatic vinyl compound units gradually increase. Isopower may be included as appropriate.
  • the polymer (C1) is known in the technical field of anion polymerization.
  • JP-B 47-28915, JP-B 47-3252, JP-B 48-2423 This is disclosed in Japanese Patent Publication No. 48-20038.
  • the weight with taper block A method for producing a coalescence is disclosed in JP-A-60-81217 and the like.
  • Adjustment of the amount of bull bonds (1, 2 and 3, 4-bond content) contained in the polymer block (C1) is N, N, ⁇ ', ⁇ , -tetramethylethylenediamine, Amines such as trimethylamine, triethylamine, diazocyclo (2, 2, 2) octane, ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, thioethers, phosphines, phosphoamides, alkylbenzene sulfonates, potassium Or sodium alkoxide.
  • Amines such as trimethylamine, triethylamine, diazocyclo (2, 2, 2) octane
  • ethers such as tetrahydrofuran
  • diethylene glycol dimethyl ether diethylene glycol dibutyl ether
  • thioethers thioethers
  • phosphines phosphines
  • phosphoamides alkyl
  • a polymer in which a polymer molecular chain is extended or branched via a coupling agent residue using a coupling agent can also be used.
  • Coupling agents used here include jetyl adipate, dibutenebenzene, methyldichlorosilane, silicon tetrachloride, butyl trichloro silicon, tetra black tin, butyl tri black tin, dimethyl black silicon, tetra black germanium, 1 1,2 dibromoethane, 1,4 chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized amateur oil, tolylene diisocyanate, 1,2,4 benzene triisocyanate and the like.
  • the content of vinyl bonds (1, 2 and 3, 4 bonds) derived from the conjugation compound in the polymer (C1) is preferably in the range of 5 to 80%.
  • the number average molecular weight of the above polymer (C1) is preferably ⁇ 10,000 to 1,000,000, more preferably ⁇ 20,000 to 500,000, more preferred ⁇ more 20 , 000 to 300,000, specially preferred ⁇ or 20,000 to 200,000.
  • the number average molecular weight is determined by gel permeation chromatography (GPC), and the same applies to the following.
  • Preferred examples of the block copolymer as the polymer (C1) include polymers having structures represented by the following formulas (IV) to (XI).
  • c 1 is a polymer block composed of a homopolymer or a copolymer containing only a conjugated diene compound unit or a conjugated diene compound unit, and further comprising an aromatic belief.
  • C 2 is a polymer block mainly containing an aromatic vinyl compound unit, and if it is a polymer block substantially having an aromatic vinyl compound, Further, a polymer block containing 90% by mass or more, more preferably 99% by mass or more of an aromatic bur compound, which may contain a partially conjugated Jen compound.
  • X is a residue of the coupling agent
  • C 11 is a polymer block mainly containing a conjugated gen compound unit, and a bull bond amount is 20% or more
  • C 12 is mainly containing a conjugated gen compound unit
  • It is a polymer block having a bulle bond amount of less than 20%
  • y is an integer of 1 to 5
  • z is an integer of 1 to 5
  • z ' is an integer of 1 to 5.
  • C 1 s when there are a plurality of C 1 s , they may be the same or different.
  • C 2 is the same. ]
  • the content of vinyl bonds (1, 2 and 3, 4 bonds) derived from the conjugated conjugated compound in the block copolymer preferable as the polymer (C1) is preferably in the range of 5 to 80%.
  • the number average molecular weight of the block copolymer is preferably 10,000 to 1,000,000, more preferably ⁇ 20, 000 to 500,000, specially preferred ⁇ It is 20, 000 to 300, 000.
  • the number average molecular weight of the polymer block c 1 (c 11 and c 12 ) is preferably 5,000 to 200,000, and the number average of the polymer block C 2
  • the molecular weight is preferably 3,000 to 150,000.
  • the use ratio of the aromatic vinyl compound and the conjugated genie compound is as follows: aromatic vinyl compound conjugated genie compound
  • ⁇ 70 ⁇ 30 ⁇ 90 mass 0/0 and more preferably the range of the preferred tool 15 ⁇ 65 ⁇ 35 ⁇ 85 mass 0/0, and particularly preferably from 20 ⁇ 60 ⁇ 40 ⁇ 80 mass 0/0.
  • block copolymers preferred from the viewpoint of impact resistance is a polymer having in the range of 1 to 10 tapered blocks in which aromatic vinyl compounds are gradually increased in block (c2), and Z or A radial block type that has been coupled.
  • polymer (C1) a commercially available product can be used, for example, “TR200 manufactured by JSR Corporation. Can use "0”, “TR2500”, “TR2600”, “TR2827” (named above, product name).
  • the polymer (C2) is a hydrogenated product of the polymer (C1). That is, the polymer (C2)
  • (C2) is obtained by hydrogenating at least a part of the carbon-carbon double bond derived from the conjugation compound unit.
  • the hydrogenation rate is preferably 10-100%, more preferably
  • polymer (C2) a force capable of using one or more of hydrogenated polymers having the structures represented by the above formulas (IV) to (XI) can be used.
  • Polymer before hydrogenation as (C1) in particular, a vinyl bond content of the polymer is preferably tool in the polymer block C 1 of the formula (VI) is 6
  • Hydrogenation to the polymer (C1) is, for example, JP-B-42-8704, JP-B-43.
  • the polymer (C2) a commercially available product can be used.
  • “DYNALON 1320P”, “DYNARON 1321P”, “DYNARON 2324P”, “DYNARON 6200P”, “DYNARON” manufactured by JSR Corporation can be used.
  • “4400P”, “Dynalon 4600P”, “Tuftec H1041” (trade name) manufactured by Asahi Kasei Co., Ltd., etc. can be used.
  • the melt mass flow rate of the component (C) is preferably used in any of the polymers (C1) and (C2). Is from 0.5 to 50 gZlO, more preferably from 1 to 20 gZlO.
  • the above polymers (C1) and (C2) can be used in combination.
  • fraction (CI) / (C2) is 0-80 mass 0 / OZl00 ⁇ 20 mass 0/0, more preferably. -60 mass 0 / oZl 00-40 mass%, more preferably 0-40 mass% Z100-60 mass%.
  • the content of component (C) is 0 to 0 when the total of component (A), component (B) and component (C) is 100% by mass. 50% by weight, preferably 0-4 0% by mass, more preferably 0-35% by mass. When this content exceeds 50% by mass, the rigidity tends to decrease. In particular, when used as a support for an adhesive film, the rigidity is lacking.
  • the antistatic resin composition of the present invention further comprises at least one antistatic property selected from the group consisting of the following component (E1), component (E2), component (E3) and component (E4): It may contain an agent (E) (also referred to as “component (E)” in the present invention). These components may be used alone or in combination.
  • Component (E1) a salt having a cation moiety having a fluorinated alkylsulfol group
  • Component (E2) a polymer containing a unit represented by the following general formula ( ⁇ ),
  • Component (E3) a boron compound containing a unit represented by the following general formula ( ⁇ ),
  • Ingredient (E4) nonionic surfactant.
  • R 5 represents a hydrocarbon group, preferably an alkylene group
  • R 5 ′ represents a hydrogen atom, a halogen atom or a hydrocarbon group
  • X represents a hydrogen atom, a hydrocarbon group, a urethane residue or an ester residue.
  • a hydrocarbon group having a group or a hydrophilic group, preferably an anionic hydrophilic group, and m represents a number of 1 or more.
  • the salt (El) having a key moiety having a fluorinated alkylsulfol group is a fluorinated alkylsulfol group.
  • the number of fluorine atoms bonded to the carbon atom of the fluorinated alkylsulfonyl group is not particularly limited, and any one of 1 to 3 fluorine atoms may be bonded to one carbon atom. Further, the number of sulfo groups is not particularly limited.
  • Examples of the fluorinated alkylsulfonyl group contained in the cation moiety include fluorinated lower alkylsulfol groups such as trifluoromethanesulfonic acid and pentafluoroethanesulfonic acid, in particular. And perfluoroalkylsulfol groups.
  • the cation constituting component (E1) is preferably trifluoromethanesulfonic acid itself, one or more of bis (trifluoromethanesulfol) imide, tris (trifluoromethanesulfonyl) methide, etc.
  • Derivatives such as methide and ammonia in which a hydrogen atom is substituted with a trifluoromethanesulfol group may be mentioned.
  • Specific examples of the key-on portion include CFSO-, (CFSO) N-, and (CFSO) C-.
  • CFSO-, (CFSO) N-, and (CFSO) C- As the cation part, Li
  • Alkali metal ions such as +, Na + and K + can be mentioned, and among these, Li + is preferable.
  • lithium trifluoromethanesulfonate bis (trifluoromethanesulfol) imide lithium, bis (trifluoromethanesulfol) imide sodium, bis (trifluoromethanesulfol) Examples include potassium imide, tris (trifluoromethanesulfol) methide lithium, tris (trifluoromethanesulfol) methide sodium, and tris (trifluoromethanesulfol) methide potassium. These can be used alone or in combination of two or more. Of these, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfol) imide and tris (trifluoromethyl). Tansulfol) Methidolithium is preferred.
  • the above component (E1) when used, it can be used as it is, dissolved in a solvent such as water, bis [2- (2-butoxyethoxy) ethyl] adipate, bis (2-butoxychetyl) phthalate, etc. It may be used in the form of a solution obtained by mixing with a polymer having an ether bond, such as the above component (B), and used in the form of a masterbatch.
  • a polymer having an ether bond include polyethylene glycol, polyethylene oxide, a block copolymer composed of a polyamide block and a polyethylene glycol block, and a block copolymer composed of a polyester block and a polyethylene glycol block.
  • the concentration is preferably in the range of 0.1 to 80% by mass, more preferably 1 to 60% by mass.
  • the component (E1) a commercially available product can be used.
  • “Sanconol AQ—50 ⁇ ” above, trade name
  • “Sanconol ⁇ -25” (trade name) manufactured by Sanko Chemical Industry Co., Ltd. can be used.
  • the component (E1) can be used alone or in combination of two or more.
  • component (E1) When component (E1) is used alone as component ( ⁇ ), the content of component ( ⁇ ) in the antistatic resin composition of the present invention is such that components (A), ( ⁇ ) and When the total of (C) is 100 parts by mass, it is preferably 0.01-30 parts by mass, more preferably 0.01-20 parts by mass, still more preferably 0.1-10 parts by mass, particularly preferably 0.1 to 5 parts by mass. If the content of this component (E1) is too large, the appearance of the molded product may be inferior, and if it is too small, the antistatic effect may not be sufficient.
  • the polymer ( ⁇ 2) (also referred to as “component ( ⁇ 2)” in the present invention) containing the unit represented by the above general formula (XII) is preferably 10 to: LOO mass. 0/0, more preferably. 20 to: LOO wt%, more preferably 30: a polymer containing LOO mass%.
  • the above units are at least 2 in the polymer constituting the component ( ⁇ 2). More than 1, preferably 3 It is preferable to contain 30 pieces.
  • R 5 is a hydrocarbon group, preferably an alkylene group having 24 carbon atoms, and particularly preferably an ethylene group.
  • R 5 ′ is a hydrogen atom, a halogen atom or a hydrocarbon group.
  • the halogen atom include a chlorine atom, a bromine atom and an iodine atom.
  • the hydrocarbon group include an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, and a cycloalkenyl group. There are no particular limitations on the number of carbon atoms in these groups.
  • alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec butyl group, a tbutyl group, an n pentyl group, an isopentinole group, and a sec pentinole group.
  • T pentinole group T pentinole group, n-hexenole group, sec hexinole group, n-heptyl group, sec heptyl group, n-octyl group, 2-ethyl hexyl group, sec octyl group, n-nor group, sec-nor group, n-decyl group, sec-decyl group, n-undecyl group, sec undecyl group, n-dodecyl group, sec dodecyl group, n tridecyl group, isotridecyl group, sec tridecyl group, n-tetradecyl group , Sec-tetradecyl group, n-xadecyl group, sec-hexadecyl group, stearyl group, icosyl group, docosyl group, tetracosyl group, triaconsyl group, 2-butyloctyl group
  • alkenyl group examples include a butyl group, a allyl group, a probe group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptul group, and an otatur group.
  • aryl group a phenyl group, a tolyl group, a xylyl group, a tertyl group, a mesityl group, a benzyl group, a phenethyl group, a styryl group, a cinnamyl group, a benzhydryl group, a trityl group, an ethylphenol group, a propylphenol group, Group, butylphenol group, pentylphenol group, Xylphenyl, heptylphenyl, octylphenyl, norphenyl, decylphenyl, undecylphenyl, dodecylphenyl, phenylphenyl, benzylphenol, styrenated Group, p-taylphenol group, dinol-phenol group, 0C naphthyl group, ⁇ -naphthyl
  • Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a methylcyclopentyl group, a methylcyclohexyl group, and a methylcycloheptyl group.
  • Examples of the cycloalkenyl group include a cyclopentyl group, a cyclohexenyl group, a cycloheptyl group, a methylcyclopentyl group, a methylcyclohexyl group, and a methylcycloheptenyl group.
  • R 5 ' is preferably a hydrogen atom, a chlorine atom, or a bromine atom, which is preferably a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 36 carbon atoms from the viewpoint of miscibility with and compatibility with resin. More preferred are alkyl groups having 1 to 24 carbon atoms and aryl groups having 2 to 24 carbon atoms.
  • X is a hydrogen atom, a hydrocarbon group, a hydrocarbon group having a urethane residue or an ester residue, or a hydrophilic group (for example, an anionic hydrophilic group).
  • the hydrocarbon group the hydrocarbon group described above as R 5 ′ can be applied. That is, an alkyl group, an alkyl group, an aryl group, a cycloalkyl group, a cycloalkenyl group and the like can be mentioned. Of these, alkyl groups having 1 to 4 carbon atoms are preferred, and alkyl groups having 1 to 4 carbon atoms are most preferred.
  • the urethane residue means an atomic group after the isocyanate group in the monoisocyanate has reacted.
  • the monoisocyanate include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, hexyl isocyanate, octyl isocyanate, lauryl isocyanate, octadecyl isocyanate, cyclohexane.
  • Examples include xyl isocyanate, phenyl isocyanate, tolylene isocyanate, and oleyl isocyanate.
  • ester group in the hydrocarbon group having an ester residue examples include a acetyl group, propionyl group, petityl group, isoptylyl group, valeryl group, isovaleryl group, bivalyl group, lauroyl group, myristoyl group, noremitoyl group, Stearoyl group, behyl group, acryl Group, propioroyl group, methacrylyl group, crotonol group, oleiroyl group, benzoyl group, phthaloyl group, succinyl group and the like.
  • an alkylsulfonic acid group C H SO M (k is an integer of 2 to 4 k 2k 3
  • Rate group CH COOM and the like.
  • M is a hydrogen atom, a metal atom, or ammonia (including quaternary ammonia).
  • M is a metal atom
  • an alkali metal atom such as lithium, sodium or potassium
  • an alkaline earth metal atom such as magnesium or calcium (however, since the alkaline earth metal atom is usually divalent, 1Z2 ) And the like.
  • sodium and potassium are preferred.
  • M is ammonia
  • its forming substances are ammonia, methylamine, dimethylamine, ethylamine, jetylamine, (iso) propylamine, di (iso) propylamine, monoethanolamine, N methylmonoethanolamine.
  • m is a number of 1 or more, preferably 1 to 300, more preferably 1 to 200, and still more preferably 5 to L00.
  • the component ( ⁇ 2) includes a unit consisting of alkylene oxide adduct (N1) of dehydration condensate of phenol or a phenol having a substituent and a formaldehyde; alkylene oxide of this compound (N1) Compound obtained by etherification of the chain end with a hydrocarbon group () 2) Unit also having a force; Compound (N3) wherein the end of the alkylene oxide chain of the compound (N1) is substituted with a hydrocarbon group having an isocyanate group or an ester group ( ⁇ 3 From the compound ( ⁇ 4) in which a terionic hydrophilic group (sulfonic acid group, sulfate group, phosphate group, carboxylate group, etc.) is introduced at the end of the alkylene oxide chain of the compound (N1) And polymers containing one or more of the above units.
  • a compound that can be co-condensed with phenol or a phenol having a substituent for example,
  • a polymer obtained by reacting one or more of the compounds (N1) to (N4) can be used as the component (E2).
  • phenol or a phenol having a substituent may be substituted with ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran (1, 4-butylene oxide), long chain a one-year-old refin oxide.
  • alkylene oxides such as styrene oxide, etc.
  • (R 5 — O) part represented by the above general formula (XII) is formed by addition polymerization of alkylene oxides, etc.
  • the type of (R 5 — ⁇ ) is determined by the type of alkylene oxide to be added.
  • the form of polymerization of added alkylene oxide or the like is not particularly limited, and homopolymerization of one type of alkylene oxide or the like, random copolymerization of two or more types of alkylene oxide, block copolymerization, or random Z block copolymerization. Any of these may be used.
  • R 5 is preferably an alkylene group having 2 to 4 carbon atoms, particularly preferably an ethylene group.
  • the (R 5 — 5 ) moiety is formed by copolymerization of two or more types of alkylene oxides, one of them is preferably ethylene oxide.
  • m is preferably 1 to 300, more preferably 1 to 200, still more preferably 5 to: L00.
  • the compound (N4) is publicly known by using a compound having a terionic hydrophilic group exemplified above for part or all of the terminal (usually a hydroxyl group) of the compound (N1). The reaction can be obtained from this method.
  • component (E2) a commercially available product can be used.
  • “Adecanol AS-113” (trade name) manufactured by Asahi Denka Kogyo Co., Ltd. can be used.
  • the component (E2) can be used alone or in combination of two or more.
  • component (E2) when component (E2) is used alone as component (E), the content of component (E) in the antistatic resin composition of the present invention is such that components (A), (B) and When the total of (C) is 100 parts by mass, it is preferably 0.01-30 parts by mass, more preferably 0.1-30 parts by mass, and still more preferably 1 to 25 parts by mass, particularly preferably 3 to 20 parts by mass. If the content of this component (E2) is too large, the appearance of the molded product may be inferior, and if it is too small, the antistatic effect may not be sufficient.
  • the boron compound (E3) (also referred to as "component (E3)" in the present invention) containing the unit represented by the above general o ( ⁇ ) is preferably represented by 90 to: LOO mass%, more preferably 95-100 mass%, still more preferably 98-: a compound containing LOO mass%.
  • (E3) is preferably a polymer compound containing at least 5 units.
  • Examples of the compound containing the unit represented by the general formula ( ⁇ ) include a semipolar organic boron polymer compound represented by the following general formula (XIV) and a total number of carbon atoms having a hydroxyl group of 5 It is preferably a polymer charge transfer conjugate which is a reaction product of one boron atom to one basic nitrogen atom with one or more of ⁇ 82 tertiary amines.
  • T 2 is
  • R 9 is a hydrocarbon group having 1 to 82 carbon atoms.
  • R 1U is a hydrocarbon group having 2 to 13 carbon atoms.
  • S, t and u are respectively
  • R 6 , R 7 and R 8 are the same or different organic groups, and r is 10 to: L 000. ]
  • examples of R 7 and R 8 include a hydrocarbon group, an alkoxy group, a phenoxy group, a benzyloxy group, and an alkylene glycol group. These groups may have a functional group such as a hydroxyl group, or may have a substituent.
  • Examples of the charge transfer-type conjugate include conjugate forces represented by the following chemical formulas (XV) to (XXII).
  • XV conjugate forces represented by the following chemical formulas
  • XXII conjugate forces represented by the following chemical formulas
  • a terminal carbon atom and oxygen atom are usually bonded to a hydrogen atom or a hydroxyl group, respectively.
  • R ′ is a residue of polybutene having an average degree of polymerization of 20.
  • the polymer charge-transfer conjugate can be produced by the method described in Japanese Patent No. 2573986.
  • component (E3) a commercially available product can be used.
  • “NOI BORON 400N” (trade name) manufactured by Boron International Co., Ltd. is preferable.
  • the above component (E3) may be blended alone in the production of the composition, or a mixture (composition) comprising the above component (A), component (B), component (C) and the like.
  • An example of the latter is “NOBOLON MB400N-8LDPE” (trade name) manufactured by Boron International, Inc., which is a master batch using polyethylene as a matrix.
  • the component (E3) can be used alone or in combination of two or more.
  • component (E3) When component (E3) is used alone as component (E), the content of component (E3) in the antistatic resin composition of the present invention is such that component (A), component (B) And when the total of component (C) is 100 parts by mass, it is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 20 parts by mass, and even more preferably 0.1 to: part by mass of LO. Particularly preferred is 0.3 to 5 parts by mass. If the content of this component (E3) is too large, the appearance of the molded product may be inferior, and if it is too small, the antistatic effect may not be sufficient.
  • nonionic surfactant (E4) also referred to as “component (E4)” in the present invention
  • component (E4) examples include esters of polyhydric alcohols, nitrogen-containing compounds, and the like.
  • ester of the polyhydric alcohol examples include glycerin ester, polyglycerin ester, sonorevitane ester, ethylene glycol ester, propylene glycol ester and the like.
  • examples of the glycerin ester include glycerin monolaurate, glycerin monomyristate, daricerine monopalmitate, glycerin monostearate, glycerin monobehenate, and glycerin monooleate.
  • polyglycerol ester examples include diglycerol monolaurate, diglycerol monomyristate, diglycerol monopalmitate, diglycerol monostearate, diglycerol monobenzoate, and diglycerol monooleate.
  • sorbitan esters include sorbitan monooleate, sorbitan monobehenate, sorbitan monostearate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, and the like.
  • Examples of the ethylene glycol ester include ethylene glycol monostearate.
  • propylene glycol ester examples include propylene glycol monostearate.
  • glycerol monostearate diglycerol monostearate, glycerol monolaurate, diglycerol monolaurate and sorbitan monostearate are preferred.
  • nitrogen-containing compounds include ammine compounds and amido compounds.
  • amine compounds include lauryl diethanolamine, myristyl diethanolamine, palmityl diethanolamine, stearyl diethanolamine, oleyljetanolamine, lauryl diisopropanolamine, myristyl diisopropanolamine, normityl diisopropanol.
  • Dialkanols such as amines, stearyldiisopropanolamines, oleyldiisopropanolamines, N, N-bishydroxyethylalkylamines (however, the carbon number of the alkyl group is usually 12-22). Min etc. are mentioned.
  • the amide compounds include lauryl diethanolamide, myristyl diethanolamide, palmityl diethanolamide, behyl-butanolamide, oleyljetanolamide, lauryl diisopropanolamide, myristyl diisopropanolamide, noremithyl diisopropanolamide. , Stearyl diisopropanolamide, and oleyl diisopropanolamide.
  • lauryl diethanolamine and stearyl diamine are preferred for the amine compound.
  • Ethanolamine is particularly preferred.
  • the above component (E4) may be incorporated alone in the production of the composition, or a mixture (composition) comprising the above component (A), component (B), component (C) and the like. ). In the latter case, miscibility can be improved in the composition.
  • the component (E4) can be used alone or in combination of two or more.
  • component (E4) When component (E4) is used alone as component (E), the content of component (D4) in the antistatic resin composition of the present invention is such that component (A), component (B) And when the total of component (C) is 100 parts by mass, preferably 0.01 to 30 parts by mass, more preferably 0.05 to 20 parts by mass, still more preferably 0.1 to: LO parts by mass, Particularly preferred is 0.5 to 5 parts by mass. If the content of this component (E4) is too large, the appearance of the molded product may be inferior, and if it is too small, the antistatic effect may be insufficient.
  • component (E4) When the above component (E4) is used, a higher alcohol having 12 to 18 carbon atoms, a lubricant, silica, calcium silicate, etc. may be blended in order to further improve the antistatic property of the component. Good.
  • a master batch can be used for the purpose of improving miscibility. In such a prescription, it is preferable to use a composition containing 20% by mass or more of component (E4).
  • a compound such as component (E4) of the present invention can be obtained as Kao's electro stripper TS-5, EA, TS-3B, TS-2B, TS-13B, TS-7B (trade name) and the like.
  • the component (E) may be a combination of two or more selected from the component (E1), the component (E2), the component (E3), and the component (E4) force. it can. Particularly preferred is a combination of the above components (E1) and (E4). Component (E1), Component (E2), Component (E3), and Component (E4) Strength When using two or more selected combinations in combination, the total amount is determined by component (A), component (B) and When the total of component (C) is 100 parts by mass, it is preferably 0.01 to 30 parts by mass, more preferably 0.01 to 15 parts by mass, still more preferably 0.1 to: part by mass of LO. Particularly preferred is 0.5 to 7 parts by mass. If the content of component (E) is too large, the appearance of the molded product may be inferior, and if it is too small, the antistatic effect may not be sufficient.
  • the antistatic resin composition of the present invention further comprises an antistatic property-imparting additive, an additive depending on the purpose and application.
  • an antistatic property-imparting additive an additive depending on the purpose and application.
  • Engineering aids fillers, antioxidants, heat stabilizers, plasticizers, fillers, UV absorbers, weathering agents, light-proofing agents, antistatic agents, flame retardants, lubricants, sliding agents, coloring agents, foaming agents, antibacterial agents
  • Additives such as nucleating agents and crystal nucleating agents can be blended.
  • an antistatic property-imparting aid in order to further improve the antistatic property by component (1), it is preferable to contain an antistatic property-imparting aid.
  • These antistatic agents can be used alone or in combination of two or more.
  • antistatic agent examples include alkali metal salts such as lithium, sodium and potassium; alkaline earth metal salts such as magnesium and calcium.
  • the types of salts include inorganic hydroacid salts (halogenated compounds), sulfates, perchlorates, etc .; carboxylates, dicarboxylates, alkane sulfonates, aromatic sulfonates ( And organic acid salts such as fluorinated sulfonic acid salts.
  • halide examples include lithium chloride, sodium chloride salt, potassium salt salt, lithium bromide, sodium bromide, potassium bromide and the like.
  • perchlorates examples include lithium perchlorate, sodium perchlorate, and potassium perchlorate.
  • Examples of the carboxylate include potassium acetate and lithium stearate.
  • alkanesulfonic acid salts include alkanesulfonic acids having 8 to 24 carbon atoms such as octylsulfonic acid, dodecylsulfonic acid, tetradecylsulfonic acid, stearylsulfonic acid, tetracosylsulfonic acid, 2-ethylhexylsulfonic acid, and the like. Salts are preferred.
  • Aromatic sulfonates include: phenyl sulfonic acid, naphthyl sulfonic acid, octyl sulfonic acid, dodecyl sulfonic acid, dibutyl sulfonic acid, dimethyl sulfonic acid, dimethyl naphthyl sulfonic acid, diisopropyl naphthyl sulfonic acid.
  • the antistatic property-imparting aid can be blended in the production of the antistatic oil composition of the present invention.
  • the blending amount of the antistatic agent is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass when the component (B) is 100 parts by mass.
  • the processing aid is not particularly limited as long as it does not impair transparency and antistatic properties.
  • an acrylic polymer, a styrene polymer, a fluorine polymer, and the like can be given. These are all preferably ultra-high molecular weight compounds (weight average molecular weight of 1 million or more), and can be used singly or in combination of two or more.
  • the amount of the processing aid is preferably 0.1 to 10 parts by mass when the total of component (A), component (B) and component (C) is 100 parts by mass. By setting this range, the compatibility of the component (A), the component (B) and the component (C) can be improved, and the extrusion moldability of the antistatic resin composition can be improved. .
  • Fillers include metals, alloys, inorganic compounds, organic compounds, polymer compounds, inorganic, organic composites, etc., powders, lumps, hollows, plates, fibers (whiskers) Etc.) can be used depending on the purpose and application. It may be conductive. These fillers can be used alone or in combination of two or more.
  • Fillers include glass fiber, glass flake, glass fiber milled fiber, glass bead, hollow glass bead, carbon fiber, carbon fiber milled fiber, aramid fiber, phenolic resin fiber, polyester fiber, zinc oxide whisker, titanium Potassium oxide whisker, aluminum borate whisker, alumina, silica, talc, calcium carbonate, wollastonite, my strength, kaolin, montmorillonite, hectorite, organically treated smectite, tin-coated titanium oxide, tin-coated silica, nickel Examples include coated carbon fiber, silver, copper, brass, iron, and vigorous black. These can be used alone or in combination of two or more.
  • the filler those treated with a known coupling agent, surface treatment agent, sizing agent or the like can be used for the purpose of improving dispersibility.
  • the coupling agent include a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent.
  • the blending amount of the filler is preferably 0.1 to 200 parts by mass when the total of the components (A), (B) and (C) is 100 parts by mass.
  • the colorant known dyes, pigments and the like can be used.
  • the blending amount of the colorant is preferably 0.001 to 20 parts by mass, more preferably 1 to 200 parts by mass when the total of the components (A), (B) and (C) is 100 parts by mass. It is.
  • the antistatic coagulant composition of the present invention may further include, as necessary, a thermoplastic coagulant, a thermoplastic elastomer, a thermosetting coagulant, etc. It may contain other polymers.
  • thermoplastic resin polyamide resin
  • polyester resin such as polybutylene terephthalate, polyethylene terephthalate, polyarylate, liquid crystalline polyester
  • polyphenylene ether such as polybutylene terephthalate, polyethylene terephthalate, polyarylate, liquid crystalline polyester
  • polyphenylene ether such as polybutylene terephthalate, polyethylene terephthalate, polyarylate, liquid crystalline polyester
  • polyphenylene ether polyphenylene sulfide
  • aromatic polycarbonate thermoplastic polyurethane
  • phenoxy resin PMMA resin, ABS resin, ASA resin, AES resin, HIPS AS resin, PS resin, MS resin, copolymer of methyl methacrylate and maleimide compound, styrene and maleimide compound And the like.
  • thermoplastic elastomers include polyamide elastomers and polyester elastomers.
  • thermosetting resin examples include epoxy resin, phenol resin, urea resin, and the like.
  • the above-described components, additives, and the like are charged into various extruders, Banbury mixers, aders, continuous rolls, rolls, etc., and melt kneaded under heating. Can be obtained. Each component may be added all at once and kneaded with force, or may be added separately and kneaded.
  • known molding methods such as injection molding, press molding, calendar molding, T-die extrusion molding, inflation molding, profile extrusion molding, and foaming molding can be applied. Further, vacuum forming or the like can be further applied to the sheet or the like obtained by the above method.
  • the antistatic resin composition of the present invention and a molded article using the same have a surface resistivity of preferably 5 x 10 12 ⁇ or less under conditions of a temperature of 23 ° C and a humidity of 50% RH. It is preferably 9 ⁇ 10 11 ⁇ or less, more preferably 9 ⁇ 10 10 ⁇ or less, and particularly preferably 5 ⁇ 10 9 ⁇ or less.
  • the shape of the molded product may be in accordance with the purpose, application, etc., such as a sheet, a film, etc.
  • Thin bodies thinness: LOOmm
  • rod-like bodies such as round bars and square bars; and further modifications thereof; trays, cases, and the like.
  • the thickness thereof is preferably 0.2 to: LOmm, more preferably 0.5 to 5 mm.
  • the thickness is preferably 5 to 200 ⁇ m, more preferably 10 to 150 ⁇ .
  • one or both sides of the sheet and film may have an uneven part, a groove part, a hole part, etc. depending on the purpose and application. Moreover, you may have a through-hole.
  • a molded article using the antistatic resin composition of the present invention is a composite article integrated with a molded article made of another material other than the single molded article, for example, an adhesive film described later, It is also suitable for forming multi-layer sheets and the like. Therefore, in the above composite article, when the antistatic resin composition of the present invention is used and the formed part is on the outermost surface, the surface specific resistance under the above conditions can be maintained. Excellent electrical properties. When the other material has transparency, the composite article as a whole is excellent in transparency.
  • the antistatic adhesive composition according to the present invention comprises 0 to 59% by mass of the above-described component ( ⁇ ) polyolefin-based resin (excluding the following component ( ⁇ )), and a block of the above component ( ⁇ ). Copolymer 3 to 60% by mass, polymer of component (C) and soot or hydrogenated product 35 to 97% by mass (provided that the above component ( ⁇ ), component ( ⁇ ) and component ( The sum of C) is 100% by mass.)
  • the component ( ⁇ ), component ( ⁇ ) and component (C) of the antistatic adhesive composition of the present invention are as described above for each component with respect to the antistatic resin composition of the present invention. Can be applied as is.
  • component (ii), component (ii) and component (C) are 0 to 40% by mass, 6 to 25% by mass and 35 to 94% by mass, respectively, preferably 0 to 35% by mass, 8 to 20% by mass and 45-92% by mass, more preferably 0-30% by mass, 8-18% by mass and 52-92% by mass, more preferably 0-25% by mass, 8-16% by mass and 59%. It is -92 mass%.
  • the adhesiveness to other members can be adjusted by selecting the type and content of component (C). That is, this Excellent tackiness is exhibited if the bull bond content contained in the polymer block (cl) forming the component (C) is preferably 60 to 90%, more preferably 70 to 85%.
  • “Dynalon 1320P”, “Dynalon 1 321P” (trade name) manufactured by JSR, etc. are preferably used.
  • the adhesiveness can be easily adjusted by appropriately blending a polymer hydrogenated product containing a polymer block (cl) having a vinyl bond content of less than 60% as part of the component (C). It becomes.
  • the content of the component (B) is too large, the appearance of the molded product may be deteriorated. If the amount is too small, the antistatic property may decrease.
  • the antistatic property may be lowered. If the amount is too small, the tackiness may not be sufficient.
  • the antistatic adhesive resin composition according to the first preferred embodiment can be suitably used to obtain a transparent film by forming a transparent adhesive layer on a support film made of polyolefin resin.
  • the component (A) is modified with polyolefin ( ⁇ '-1) and ⁇ or a functional group, and the polyolefin ( ⁇ '-2), wherein the component (C) is a hydrogenated product of a polymer mainly composed of a conjugated genie compound unit and an aromatic beryl compound unit, and the component ( ⁇ ) 0 to 59 mass %,
  • the above component ( ⁇ ) 3 to 60% by mass, and the above component (C) 40 to 97% by mass an antistatic adhesive resin composition is provided.
  • the antistatic adhesive resin composition according to the second preferred embodiment is suitably used to obtain a transparent film by forming a transparent adhesive layer on a support film having various polymer strengths such as styrene resin. it can.
  • the component (A) in the antistatic 'adhesive resin composition according to this second preferred embodiment is a polyolefin resin ( ⁇ '-1) and a polyolefin resin modified with a resin or functional group ( ⁇ '). — 2) There will be power.
  • Polyolefin resin ( ⁇ '-1) is a modified polyolefin resin, and the content of the polyolefin resin ( ⁇ ) described in the above antistatic resin composition of the present invention is as follows. all Applicable, a polymer containing at least one olefin having at least 2 carbon atoms: LO as a constituent monomer unit is preferred, and a polymer containing ethylene as a main component is particularly preferred.
  • the polyolefin resin ( ⁇ '-1) has a molecular weight sufficient as a molding resin at room temperature.
  • the melt flow rate measured according to JIS 6922 is preferably 0.01 to: LOOgZlO content, more preferably 0.03 to 70 gZlO content. belongs to.
  • the polyethylene used here any of high density polyethylene, low density polyethylene, and linear low density polyethylene can be used.
  • the above component ( ⁇ '-2) is a polyolefin modified with a functional group. It is fat.
  • the polyolefin resin is polypropylene or polyethylene, more preferably low molecular weight polypropylene or low molecular weight polyethylene, and particularly preferably low molecular weight polyethylene.
  • the weight average molecular weight of the low molecular weight polyolefin is preferably 1,000 to 100,000, more preferably ⁇ 5,000 or 6,000 to 60,000, specially preferred ⁇ or 8,000 to 50,000, 000.
  • the low molecular weight polyolefin can be obtained from a polymerization method or a thermal degradation method of high molecular weight polyolefin. The ones that are preferred due to their functional modification are those obtained by the thermal degradation method.
  • the low molecular weight polyolefin by thermal degradation is, for example, a method in which high molecular weight polyolefin is thermally degraded in an inert gas, usually at 300 ° C. to 450 ° C. for 0.5 hours to 10 hours (for example, JP-A-3- No. 62804).
  • Modification methods using functional groups include unsaturated acids, unsaturated acid anhydrides, epoxy group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, oxazoline group-containing unsaturated compounds, amino group-containing unsaturated compounds, substitution This is a method of adding an amino group-containing unsaturated compound or the like.
  • Preferred are unsaturated acids and unsaturated acid anhydrides.
  • unsaturated acid used here examples include acrylic acid, methacrylic acid, crotonic acid, ketonic acid, itaconic acid, maleic acid, and the like. These may be used alone or in combination of two or more. Can be used. Further, as the unsaturated acid anhydride, there are maleic anhydride, itaconic anhydride, black mouth itaconic anhydride, black mouth maleic anhydride, citraconic anhydride, etc. These can be used alone or in combination of two or more. Preferred is maleic anhydride.
  • the amount of the functional group-containing unsaturated compound in the above component 2) is preferably 0.5 to 25% by mass, more preferably 1 to 20% by mass, particularly preferably 100% by mass of polyolefin resin. 1 to 15% by mass.
  • the modification method using the functional group-containing unsaturated compound can be obtained, for example, by modifying the functional group-containing unsaturated compound in a polyolefin resin by a method such as a solution method or a melting method in the presence of an organic peroxide if necessary. Can do.
  • the material corresponding to the above component ( ⁇ ′-2) can be obtained on the market as, for example, Yumetus 1001, 1003, 1010, 100TS, HOTS, 2000, CA60 (trade name) manufactured by Sanyo Chemical Industries.
  • the above component ( ⁇ '-1) is used for the purpose of adjusting the tackiness of the pressure-sensitive adhesive.
  • the above component ( ⁇ '-2) is used for the purpose of improving the adhesion between the pressure-sensitive adhesive and the support when producing the pressure-sensitive adhesive film, and the easy-adhesive coated on the support. .
  • the amount of the component ( ⁇ ) used is 100 mass in total of the components ( ⁇ ) and ( ⁇ ) of the present invention. % In the range of 0 to 59% by weight, preferably 1 to 59% by weight, more preferably 1 to 48% by weight, even more preferably 2 to 45% by weight, particularly preferably 3 to 40% by weight. is there.
  • the preferred amounts of the component ( ⁇ '-1) and the component ( ⁇ '-2) are both ( ⁇ 2) to 37% by mass, more preferably 2 to 35% by mass, and particularly preferably 5 to 30% by mass with respect to 100% by mass of the total of component ()) and component (ii) (C).
  • the adhesive adjustment function is poor, and if it exceeds the range, the stickiness is poor.
  • the component ( ⁇ ′-2) is less than the above range, adhesion such as adhesion between the pressure-sensitive adhesive and the support when producing an adhesive film, adhesion between the easy-adhesive coated on the support and the like If the improvement is not sufficient and the range is exceeded, the tackiness tends to be inferior, which is not preferable.
  • the component ( ⁇ ) is a block copolymer containing an olefin polymer block and a hydrophilic polymer block.
  • the above description regarding the antistatic oil-absorbing composition is applicable as it is.
  • the above components ( ⁇ ) is a block copolymer containing an olefin polymer block and a hydrophilic polymer block.
  • the amount of B) used is 3 to 60% by weight, preferably 3 to 50% by weight, based on the total 100% by weight of component (B) and component (C) when component (A) is not included.
  • the content is preferably 5 to 40% by mass, and particularly preferably 5 to 35% by mass. When the content is less than 3% by mass, the antistatic property is inferior, and when it exceeds 60% by mass, the tackiness is lowered.
  • the amount of component (B) used is 3 to 60% by mass, preferably 100% by mass of component (A), component (B) and component (C), preferably 3 to 59% by mass, more preferably 3 to 49% by mass, still more preferably 5 to 48% by mass, and particularly preferably 5 to 42% by mass. If it exceeds the mass%, the adhesiveness will decrease.
  • the component (C) comprises the component (C) as a conjugate conjugated compound unit and an aromatic vinyl compound. It is a hydrogenated product of a polymer mainly composed of units, and the contents described with respect to the antistatic resin composition of the present invention apply as it is.
  • component (C) of the antistatic adhesive resin composition of this second preferred embodiment the aromatic belieu compound unit and the conjugated genie compound unit are random copolymers, It is also possible to use a block copolymer in which each block is a block, or to form a combined form in which a random copolymer and a block copolymer are mixed.
  • a preferred component (C) is a hydrogen of a block copolymer containing a polymer block (cl) mainly composed of conjugated diene compound units and a polymer block (c2) mainly composed of aromatic beryl compound units. It is an additive.
  • the structure particularly preferred as the component (C) is as follows: In view of the ease of adjusting the adhesive strength and the ease of developing transparency as an adhesive, it has the structure of (VII) above.
  • the hydrogenated product as the component (c) of the antistatic adhesive resin composition of the second preferred embodiment is mainly hydrogenated at least part of the carbon-carbon double bond of the conjugation compound. Is. That is, as the component (C), one obtained by partially or completely hydrogenating the carbon-carbon double bond of the conjugation moiety of the copolymer described above is used.
  • the preferred hydrogenation rate is 10 to: LOO%, more preferably 50 to: L00%, and particularly preferably 90 to 100%.
  • the amount of component (C) used is that when component (A) is not included, component (B) and component (C) In the total of 100% by mass, 40 to 97% by mass, preferably 50 to 97% by mass, more preferably 60 to 95% by mass, and particularly preferably 65 to 95% by mass. When the amount exceeds 97% by mass, the antistatic property is poor.
  • the amount of component (C) used when it contains component (A) is 40 to 97% by mass, preferably 50 to 97% of the total of 100% by mass of component (A), component (B) and component (C).
  • the mass% is more preferably 50 to 93% by mass, particularly preferably 55 to 92% by mass. If it is less than 40% by mass, the tackiness is lowered, and if it exceeds 97% by mass, the antistatic property is inferior.
  • the antistatic adhesive rubber composition according to the first and second embodiments further includes a component (E) and various additives that can be blended in the antistatic resin composition of the present invention.
  • component (E) various additives that can be blended in the antistatic resin composition of the present invention.
  • other polymers can be contained.
  • the description of the antistatic resin composition of the present invention can be applied to these types and contents as they are.
  • the antistatic pressure-sensitive adhesive composition of the present invention comprises the above components (A), (B), (C), additives and the like in various extruders, Banbury mixers, aders, continuous -It can be obtained by putting it in a roll or roll and melt-kneading under heating. Each component may be mixed and then kneaded, or may be divided and added.
  • known molding methods such as injection molding, press molding, calendar molding, T-die extrusion molding, inflation molding, profile extrusion molding, and foam molding can be applied. Further, vacuum forming or the like can be further applied to the sheet or the like obtained by the above method.
  • the antistatic 'adhesive resin composition of the present invention and a molded article using the same have a surface resistivity at a temperature of 23 ° C and a humidity of 50% RH, preferably 5 X 10 12 ⁇ . Or less, more preferably 9 ⁇ 10 11 ⁇ or less, further preferably 9 ⁇ 10 10 ⁇ or less, particularly preferably 5 ⁇ 10 9 ⁇ or less It can be.
  • the shape of the molded product can be determined according to the purpose, application, etc., and thin sheets such as sheets and films; rod-shaped bodies such as round bars and square bars; can do.
  • the thickness thereof is preferably 0.2 to: LOmm, more preferably 0.5 to 5 mm.
  • the thickness is preferably 5 to 200 ⁇ m, more preferably 10 to 150 ⁇ .
  • one or both sides of the sheet and film may have an uneven part, a groove part, a hole part, etc. depending on the purpose and application. Moreover, you may have a through-hole.
  • a molded article using the antistatic adhesive pressure-sensitive resin composition of the present invention is also suitable for forming a composite article integrated with a molded article made of another material, for example, a multilayer sheet described later. is there. Therefore, in the above composite article, when the molded part using the antistatic adhesive adhesive composition of the present invention is on the outermost surface, the surface resistivity can be maintained under the above conditions. Excellent antistatic and adhesive properties. Further, when the other materials have transparency, the composite article as a whole is excellent in transparency.
  • the antistatic adhesive resin composition of the present invention can be used to form an adhesive layer on a support composed of various thermoplastic polymer compositions.
  • a support composed of various thermoplastic polymer compositions and the antistatic adhesive resin composition of the present invention which is disposed on at least one surface side of the support.
  • An adhesive film comprising the antistatic adhesive layer is provided.
  • thermoplastic polymers that can be used as the composition constituting the support generally include elastomers, rubbers and rosins. These can be used alone or in combination of two or more.
  • elastomers include olefin elastomers; styrene elastomers such as styrene 'butadiene' styrene block copolymers and styrene 'isoprene' styrene block copolymers; polyester elastomer elastomers; urethane elastomers; Polyvinyl chloride elastomer; Poly Examples include amide elastomers; fluoro rubber elastomers and the like. These can be used alone or in combination of two or more.
  • Examples of rubbers include polybutadiene, polyisoprene and other gen-based rubbers, styrene 'butadiene (block) copolymers, styrene' isoprene (block) copolymers, acrylonitrile 'butadiene copolymers, butadiene' (metabolites).
  • Acrylic acid ester copolymer hydrogenated styrene 'butadiene block copolymer, hydrogenated butadiene-based polymer, ethylene' a-olefin copolymer, ethylene ' a- olefin-polyethylene copolymer, acrylic rubber, silicone rubber , Fluorine rubber, butyl rubber, ethylene ionomer and the like.
  • the styrene / butadiene block copolymer and the styrene / isoprene block copolymer include those having an AB type, ABA type, tapered type, or radial teleblock type structure.
  • the hydrogenated butadiene polymer is a hydride of a polymer having a styrene block and a styrene / butadiene random copolymer block, and a 1,2-vinyl bond, in addition to the hydride of the block copolymer. Examples include hydrides of polymers composed of polybutadiene blocks having a content of 20% by mass or less and polybutadiene blocks having a 1,2-bule bond content of more than 20% by weight.
  • the above rubbers can be used alone or in combination of two or more.
  • Thermoplastic resins include polyolefin resins such as polyethylene and polypropylene, acrylic resins such as polymethyl methacrylate, polystyrene, styrene resins such as rubber-reinforced styrene resin, polyethylene terephthalate, Polyester resin such as polybutylene terephthalate, polyamide resin such as nylon 6, nylon 66, nylon 46, polycarbonate resin, fluorine resin, polysulfone, polyphenylene sulfide, liquid crystal polymer and the like. These can be used alone or in combination of two or more. Of these, polyolefin resins, acrylic resins, styrene resins, polyester resins, polyamide resins and polycarbonate resins are particularly preferred. Polyolefin resins and styrene resins are preferred. .
  • the polyolefin resin composition useful as a molding material for the support is not particularly limited as long as it contains a polyolefin resin, and may be only a polyolefin resin, or a polyolefin resin. A mixture of fat and other ingredients (additives, other polymers, etc.) May be. In the latter case, the antistatic resin composition of the present invention may be used as it is, or other composition may be used. When antistatic properties are required, it is particularly preferable to use the antistatic resin composition of the present invention.
  • the polyolefin resin is a homopolymer of olefins having 2 or more carbon atoms, a copolymer of two or more ⁇ -olefins, and a copolymer of ⁇ -olefin and other bur monomers.
  • low density polyethylene LDPE
  • medium density polyethylene high density polyethylene
  • HDPE high density polyethylene
  • UHMPE ultra high molecular weight polyethylene
  • ethylene propylene, 1-butene, 1 pentene, 1-hexene, 4-methinole 1-Pentene, 1-Otaten, 1-decene, etc., C3-C12 (Copolymer with X-olefins; Polypropylene (PP); Propylene, 1-butene, 1-pentene, 1-hexene, 4— Copolymers with ⁇ -olefins having 4 to 12 carbon atoms such as methyl 1-pentene, 1-octene, 1-decene; polyolefin resin that can be blended in the antistatic resin composition of the present invention (A — Ethylene / cyclic olefin copolymers, propylene / cyclic olefin copolymers; ethylene 'propylene' gen copolymers;
  • the component (A) contained in the antistatic resin composition of the present invention may be used, and the component (A) and the component (B) may be used in combination.
  • the antistatic property of the support and the antistatic property as an adhesive film are excellent.
  • polyethylene, polypropylene, propylene and ethylene copolymers are preferred polymers containing 50% by mass or more of propylene units based on the total monomer units, that is, polypropylene, propylene and ethylene copolymers. Coalescence is more preferred.
  • a power random copolymer having a random copolymer, a block copolymer and the like is particularly preferable. Further, these polymers and the above antistatic resin of the present invention.
  • Heat resistance as an adhesive film can be achieved by combining ethylene 'cyclic polyolefin copolymer, propylene' cyclic polyolefin copolymer, etc., contained in the polyolefin resin (A-1) that can be blended in the composition. Even better.
  • this polyolefin resin (A-1) force is 40% by mass or more (preferably 50% by mass or more, more preferably 60% by mass or more) with respect to the above support, 70 ° C or more At a temperature (preferably 80 ° C. or higher, more preferably 90 ° C. or higher), a support that does not undergo deformation such as warping or twisting can be obtained.
  • the styrene-based resin composition useful as a molding material for the support is not particularly limited as long as it contains a styrene-based resin, and may be only a styrene-based resin, It may be a mixture with other components (additives, other polymers, etc.).
  • Styrenic resin (D) (also referred to as “component (D)” in the present invention) is obtained by polymerizing a monomer component containing an aromatic vinyl compound in the presence of a rubbery polymer.
  • This is a resin obtained by polymerizing a monomer component containing an aromatic vinyl compound in the absence of resin and Z or rubber polymer.
  • the rubber polymer include polybutadiene, polyisoprene, styrene'butadiene (block) copolymer, styrene'isoprene (block) copolymer, acrylonitrile 'butadiene copolymer, and butadiene (meth) acrylate.
  • Copolymer hydrogenated styrene 'butadiene block copolymer, hydrogenated butadiene polymer, ethylene' a-olefin copolymer (eg, ethylene 'propylene copolymer, ethylene' propylene, non-conjugated gen copolymer) , Ethylene.butene-1 copolymer, ethylene'butene-1 non-conjugated gen copolymer, etc.), ethylene'a-olefin'polyene copolymer, acrylic rubber, silicone rubber, silicone 'acrylic IPN rubber A polymer block mainly composed of aromatic beryl compounds described in the above component (C), and A block copolymer containing a polymer block mainly composed of conjugation and a hydrogenated product thereof.
  • ethylene' a-olefin copolymer eg, ethylene 'propylene copolymer, ethylene' propylene, non-conjugated gen copolymer
  • polystyrene-based resin those containing a rubbery polymer having a flexible surface when used as a support film are preferable.
  • rubbery polymer content in the styrene-based ⁇ is a styrene ⁇ to 100 mass 0/0, preferably 3-80% by weight. More preferably, it is 5-70 mass%, Most preferably, it is 10-60 mass%.
  • the gel content of the rubber polymer is not particularly limited, but when a rubber polymer is obtained by emulsion polymerization, the gel content is preferably 98% by mass or less, more preferably 40 to 98 mass 0. / 0 . Within this range, the appearance when formed into a film is excellent.
  • the said gel content rate can be calculated
  • gel content (mass 0/0) [ ⁇ W2 (g) -Wl (g) ⁇ / l (g)] X 100 ⁇ ⁇ (1)
  • the gel content is adjusted by appropriately setting the type and amount of the molecular weight regulator, the polymerization time, the polymerization temperature, the polymerization conversion rate, etc. during the production of the rubbery polymer.
  • Examples of the aromatic vinyl compound constituting the vinyl monomer used in the styrene-based resin include styrene, ⁇ -methylstyrene, hydroxystyrene, and the like. These may be used alone or in combination. Two or more types can be used in combination. Of these, styrene and ⁇ -methylstyrene are preferred.
  • bull monomers copolymerizable with aromatic beryl compounds include vinylcyan compounds, (meth) acrylic acid ester compounds, maleimide compounds, and other functional group-containing unsaturated compounds. Compounds and the like.
  • a styrene-based resin used as a support for a protective film for a display device which is one of the objects of the present invention, a preferable vinyl monomer that is preferably used for transparency is aromatic.
  • One or two or more compounds selected from the group consisting of vinyl cyanide compounds and maleimide compounds are used in combination, as required, with an aromatic vinyl ester compound and a (meth) acrylic acid alkyl ester compound as essential components.
  • at least one of various other functional group-containing compounds is used in combination.
  • unsaturated functional group-containing unsaturated compounds include unsaturated acid compounds and epoxy group-containing Examples thereof include unsaturated compounds, substituted or unsubstituted amino group-containing unsaturated compounds, and oxazoline group-containing unsaturated compounds.
  • the above other various functional group-containing unsaturated compounds can be used alone or in combination of two or more.
  • Examples of cyanobi-louis compounds used here include acrylonitrile, methacrylonitrile, etc., and these can be used alone or in combination of two or more. .
  • a cyan compound When a cyan compound is used, chemical resistance can be imparted.
  • the amount used is preferably 1 to 60% by mass, more preferably 5 to 50% by mass in the monomer component.
  • (meth) acrylic acid ester compounds include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, and the like. These may be used alone or in combination of two or more. Can be used. Particularly preferred are methyl methacrylate, in the case of using polybutadiene as the rubber polymer, Toru range of usage 20 ⁇ 30Z70 ⁇ 80 wt% styrene Z main methacrylic acid methyl (total 100 mass 0/0) A styrene-based resin having excellent lightness can be obtained.
  • maleimide compounds include maleimide, ⁇ -maleimide, ⁇ -cyclohexylmaleimide, and the like. These may be used alone or in combination of two or more.
  • maleic anhydride may be copolymerized and subsequently imidized.
  • heat resistance is imparted.
  • the amount used is preferably 1 to 60% by mass, more preferably 5 to 50% by mass in the monomer component.
  • unsaturated acid compounds include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and the like. These may be used alone or in combination. A combination of the above can be used.
  • epoxy group-containing unsaturated compound examples include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and the like. These may be used alone or in combination of two or more.
  • hydroxyl-containing unsaturated compounds examples include 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3 Hydroxy 1-methyl 1-propene, 2 Hydroxyethyl methacrylate, 2 Hydroxetyl acrylate, N- (4-Hydroxyphenol) maleimide, and so on. Or two or more types can be used in combination.
  • Examples of the acid anhydride group-containing unsaturated compound include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These may be used alone or in combination of two or more. I'll do it.
  • oxazoline group-containing unsaturated compound examples include bruoxazoline, and these can be used alone or in combination of two or more.
  • substituted or unsubstituted amino group-containing unsaturated compounds include aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, phenylaminoethyl methacrylate, N-biethylethylamine, N-acetylethylamine, acrylamine. , Methacrylamine, N-methylacrylamine, acrylamide, N-methylacrylamide, p-aminostyrene, etc., and these can be used alone or in combination of two or more.
  • the amount of the above other various functional group-containing unsaturated compounds used is the total amount of the functional group-containing unsaturated compounds used in the styrene-based resin, and is 0.1 to 20 with respect to the entire styrene-based resin. 0.1% to 10% by mass is more preferable.
  • the styrene-based resin of the present invention can be produced by a known polymerization method, for example, emulsion polymerization, bulk polymerization, solution polymerization, suspension polymerization, or a combination of these.
  • a known polymerization method for example, emulsion polymerization, bulk polymerization, solution polymerization, suspension polymerization, or a combination of these.
  • preferred polymerization methods for a polymer obtained by (co) polymerizing a vinyl monomer in the presence of a rubbery polymer are emulsion polymerization and solution polymerization.
  • preferred polymerization methods for polymers obtained by (co) polymerizing vinyl monomers in the absence of rubbery polymers are bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. .
  • a polymerization initiator In the case of producing by emulsion polymerization, a polymerization initiator, a chain transfer agent, an emulsifier and the like are used, and all of these known ones can be used.
  • tamennoide mouth peroxide As polymerization initiators, tamennoide mouth peroxide, p-menthannoide mouth peroxide, diisopropylbenzene hydride mouth peroxide, tetramethylbutyl hydride mouth peroxide, tert-butyl hydride mouth peroxide, potassium persulfate, azobisisobutane Chiguchi-Trill and the like.
  • redox systems such as various reducing agents, sugar-containing iron pyrophosphate formulations, sulfoxylate formulations, etc. as polymerization initiation aids.
  • chain transfer agent examples include octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-xyl mercaptan, terpinolene and the like.
  • the emulsifier examples include alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, aliphatic sulfonates such as sodium lauryl sulfate, higher fatty acid salts such as potassium laurate, potassium stearate, potassium oleate, and potassium palmitate.
  • alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate
  • aliphatic sulfonates such as sodium lauryl sulfate
  • higher fatty acid salts such as potassium laurate, potassium stearate, potassium oleate, and potassium palmitate.
  • a rosinate such as potassium rosinate can be used.
  • the method of using the rubbery polymer and the bull monomer may be carried out by adding a vinyl monomer all at once in the presence of the total amount of the rubbery polymer. It may be polymerized by dividing or continuously adding. A part of the rubber polymer may be added during the polymerization.
  • the obtained latex after emulsion polymerization is usually coagulated with a coagulant, washed with water and dried to obtain a styrene-based resin powder.
  • a coagulant used here, inorganic salts such as calcium chloride, magnesium sulfate and magnesium chloride, or acids such as sulfuric acid, hydrochloric acid, acetic acid, citrate and malic acid can be used.
  • Solvents that can be used in the production of styrene-based resins by solution polymerization are inert polymerization solvents that are used in ordinary radical polymerization, for example, aromatic hydrocarbons such as ethylbenzene and toluene. , Ketones such as methyl ethyl ketone and acetone, acetonitrile
  • the polymerization temperature is preferably in the range of 80 140 ° C, more preferably 85 120 ° C.
  • a polymerization initiator may be used, or polymerization may be performed by thermal polymerization without using a polymerization initiator.
  • Polymerization initiators include ketone peroxide, dialkyl peroxide, disilver oxide, peroxyester, hydrated peroxide, azobisisobutyronitrile, benzoyl peroxide, 1, ⁇ -azobis (cyclohexane-1—power (Both-tolyl) and the like are preferably used.
  • a chain transfer agent for example, mercaptans, terpinolenes, OC-methylstyrene dimer, etc. can be used.
  • the polymerization initiator, chain transfer agent, etc. described in the solution polymerization can be used.
  • the amount of monomer remaining in the styrene-based resin obtained by the above polymerization method is preferably 10, OOOppm or less, more preferably 5, OOOppm or less.
  • a styrene-based resin obtained by polymerizing a butyl monomer in the presence of a rubbery polymer is usually a copolymer obtained by graft-copolymerizing the vinyl monomer to a rubbery polymer. And grafted to a rubbery polymer, and contains an ungrafted component (the (co) polymer of the vinyl monomer).
  • the styrene-based resin obtained by polymerizing a bulu monomer in the presence of a rubber polymer preferably has a draft rate of 20 to 200% by mass, more preferably 30 to 150% by mass, and particularly preferably. It is 40-120 mass%, and a graft ratio can be calculated
  • T represents styrene-based lg obtained by polymerizing a bulu monomer in the presence of a rubbery polymer, and the mixture is shaken with a shaker for 2 hours in 20 ml of acetone.
  • the intrinsic viscosity [ ⁇ ] (measured at 30 ° C using methyl ethyl ketone as the solvent) of the acetone-soluble component of the component related to the styrene-based resin of the present invention is preferably 0. 2 to 1.2 dlZg, more preferably 0.3 to 1 Odl / g, and particularly preferably 0.3 to 0.8 dl / g.
  • the average particle size of the grafted rubber polymer particles dispersed in the styrene-based resin obtained by polymerizing the vinyl monomer in the presence of the rubber polymer is preferably 500 to 30,000 OA. This is in the range of ⁇ 10000 or 20,000 to 2,000 mm, especially in the range of ⁇ 500 or more to 1,500 to 8, or ⁇ .
  • the average particle diameter can be measured by a known method using an electron microscope.
  • the composition constituting the support may be a thermoplastic polymer alone or may contain an antistatic agent.
  • the amount of antistatic agent used is the sum of thermoplastic polymer and antistatic agent 1 When it is 00 mass%, it is 3-30 mass%, Preferably it is 5-25 mass%, More preferably, it is 8-20 mass%, Most preferably, it is 10-20 mass%. If the amount used is less than 3% by mass, the desired antistatic property cannot be obtained. If it exceeds 30% by mass, a uniform film cannot be obtained.
  • the antistatic agent is not particularly limited. A known antistatic agent can be used. A preferable antistatic agent is one that does not impair transparency when an antistatic agent is added.
  • the antistatic agent (F) also acts as a polyamide block (F-2-1) and a hydrophilic polymer block (F-2-2).
  • Polyamides used here include ethylene diamine, tetramethylene diamine, hexamethylene diamine, decamethylene diamine, 2, 3, 4 or 2, 4, 4-trimethylene hexamethylene diamine, 1 , 3 or 1,4-bis (aminomethyl) cyclohexane, bis (p-aminohexyl) methane, phenoldiamine, m-xylenediamine, p-xylendiamine, aliphatic, alicyclic, or aromatic Polyamides, force prolactams derived from diamine components such as diamine and aliphatic, alicyclic or aromatic dicarboxylic acids such as adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, polyamide obtained by
  • hydrophilic polymer block (F-2-2) used here any of those described for the hydrophilic polymer block (b2) can be used.
  • This preferred polymerization method of the antistatic agent (F) is a heat melt polymerization method, and specific examples thereof are shown below.
  • a particularly preferable method is the method (i).
  • alkali metal and Z or alkaline earth metal salts (H) described in the explanation of the polymer block (b2) can be used.
  • Examples of the dicarboxylic acid used to carboxylate the molecular ends of the polyamide component include adipic acid, suberic acid, sebacic acid, maleic acid, citraconic acid, maleic anhydride, citraconic anhydride, and cyclohexane.
  • Examples include dicarboxylic acid, terephthalic acid, and isophthalic acid.
  • the number average molecular weight of the polyamide of the present invention is preferably in the range of 500 to 20,000, more preferably 500 to 10,000, particularly preferably 500 to 5,000. S The object of the present invention is achieved. In addition, it is preferable.
  • the mass ratio (F—2-1ZF—2-2) of the polyamide block (F—2-1) and the hydrophilic polymer block (F—2-2) is 90Z 10 to 10Z90. It is more preferable that it is in the range of 80Z20 to 20Z80, particularly preferably 70 to 30 to 70.
  • the molecular weight of the antistatic agent (F) is not particularly limited, but the reduced viscosity (7? Sp / C) (measured in formic acid solution, 0.5gZl00ml, 25 ° C) is in the range of 1 to 3dlZg More preferably, it is 1.2 to 2.5 dlZg.
  • antistatic agent (F) can be used alone or in combination of two or more.
  • the antistatic agent (F) is available as Pelestat NC6321, M-140 (trade name) manufactured by Sanyo Chemical Industries.
  • thermoplastic polymer can be obtained by various extruders, Banbury mixers, aders, continuous-kinders, rolls, and the like.
  • the thickness of the film is preferably 10 to 200 m from the viewpoint of handling.
  • This film is known It is preferable to use the calendar method, T-die method, inflation method, etc.
  • thermoplastic polymers include known weathering (light) agents, antioxidants, lubricants, plasticizers, colorants, dyes, foaming agents, processing aids (ultra high molecular weight acrylic polymers, ultra high molecular weight polymers). Molecular weight styrene polymer) and the like can be appropriately blended.
  • the antistatic adhesive pressure-sensitive resin composition of the present invention it is preferable to use a polyolefin-based resin composition as the thermoplastic polymer composition constituting the support.
  • a polyolefin-based resin composition As the polyolefin resin composition, the use of the antistatic resin composition of the present invention is preferred from the viewpoint of the antistatic property of the adhesive film (first embodiment of the adhesive film).
  • thermoplastic polymer composition constituting the support. Second embodiment).
  • Examples of the adhesive film using the antistatic adhesive resin composition of the first embodiment of the present invention include a support (hereinafter referred to as “support (1)”) having only the component (A).
  • An embodiment comprising an antistatic adhesive layer [i], a support (hereinafter referred to as “support (2)”) also having an antistatic resin composition power of the present invention, and an antistatic adhesive layer.
  • composition constituting the support (3) in the above embodiment [iii] it contains the component (A) and the component (C), and does not contain the component (B)! ⁇ Composition; contains component (B) and component (C) and does not contain component (A)! ⁇ Composition; contains component (A) and other than component (B) and component (C) A composition containing component (B), a component containing component (B) and other components other than component (A) and component (C); a polyolefin system other than component (A) and component (B) Examples include compositions containing rosin.
  • the supports (2) and (3) may contain an additive additive that can be blended in the antistatic resin composition of the present invention.
  • the content of the additive is that of the present invention.
  • the description in the antistatic oil-absorbing composition can be applied.
  • the content of the additive is the total amount of the components (A), (B) and (C) in the antistatic resin composition of the present invention, and the polyolefin.
  • the amount described in the antistatic oil composition of the present invention can be applied by replacing the total amount of the system oil composition.
  • the antistatic resin composition of the present invention (the above embodiment [ii]) is preferable.
  • the component (as component (A-1) and component (A-2) it is preferable to use the component (as component (A-1) and component (A-2) as a combination).
  • the thickness of the support of the pressure-sensitive adhesive film is preferably 10 to 200 111, more preferably 10 to: LOO ⁇ m.
  • a portion where the antistatic adhesive layer is disposed may have a groove, a concave portion, a convex portion, or the like.
  • the thickness of the antistatic adhesive layer is preferably 1 to: LOO ⁇ m, more preferably 5 to 50 ⁇ m.
  • the thickness of the antistatic adhesive layer is usually smaller than the thickness of the support.
  • the antistatic adhesive layer may be on one side of the support or on both sides. In the latter case, it is a double-sided adhesive film. Further, it may be a part of each surface or the entire surface.
  • the first and second embodiments of the above-mentioned pressure-sensitive adhesive film are also excellent in adhesiveness between the support and the antistatic pressure-sensitive adhesive layer, and also the surface of the support and the antistatic pressure-sensitive adhesive layer.
  • the peel strength according to the conditions in Examples described later can be preferably 3 OOgZl5 mm or more, more preferably 400 gZl5 mm or more, and even more preferably 500 gZl5 mm or more.
  • antistatic properties surface resistivity under conditions of temperature 23 ° C and humidity 50% RH
  • 5 X 10 12 ⁇ or less preferably 5 X 10 12 ⁇ or less, more preferably 9 X 10 11 ⁇ or less, depending on the support surface. More preferably, it is 9 ⁇ 10 10 ⁇ or less, and particularly preferably 5 ⁇ 10 9 ⁇ or less.
  • the adhesive film of the present invention can be provided with a protective layer on the surface of the antistatic adhesive layer for the purpose of protecting the antistatic adhesive layer and the like.
  • the constituent material of the protective layer is not particularly limited, but when peeled off, the antistatic adhesive layer is A material having a material strength that is less likely to be damaged is preferable.
  • a material having a material strength that is less likely to be damaged is preferable.
  • Specific examples include a polyester film such as polyethylene terephthalate (PET), a polypropylene film, a styrene-based resin, a resin film, and a polyamide film.
  • An adhesive film 1 in FIG. 1 includes a support 11 and an antistatic adhesive layer 12 disposed on one surface of the support 11.
  • the adhesive film 1 ′ in FIG. 2 includes a support 11, an antistatic adhesive layer 12 disposed on the surface of the support 11, and a protective layer 13 disposed on the surface of the antistatic adhesive layer 12. Is provided.
  • the adhesive film 1 "in FIG. 3 is disposed on the surface of the support 11, the antistatic adhesive layers 12a and 12b disposed on both surfaces of the support 11, and the antistatic adhesive layers 12a and 12b.
  • the pressure-sensitive adhesive film can be produced by a known method, and the production method is not particularly limited.
  • thermoplastic polymer composition such as a polyolefin resin composition or a styrene resin composition and the antistatic adhesive resin composition of the present invention are coextruded.
  • the manufacturing method of an adhesive film provided with the process to do is suitable.
  • Specific methods of coextrusion include a T-die method and an inflation method.
  • Each composition is normally used in a molten state.
  • the temperature during processing is usually selected from the melting temperature, melt viscosity, etc. of each composition in consideration of the shape, thickness, etc. of the molded product.
  • thermoplastic polymer composition and an antistatic adhesive composition obtained by previously melt-kneading the adhesive resin composition by the above method may be used
  • Thermoplastic polymer composition and antistatic 'A mixture of the components of the adhesive resin composition may be melt kneaded at the time of coextrusion.
  • Thermoplastic polymer composition and antistatic' The components of the adhesive resin composition may be added at the time of coextrusion, and a method in which the above (1), (2), and (3) are combined may be used.
  • thermoplastic polymer composition a polyolefin resin composition, a styrene resin composition, etc. can be used conveniently.
  • the preferred method for obtaining the pressure-sensitive adhesive film of the present invention by coextrusion is thermoplasticity as a support.
  • the polymer composition is prepared by melt kneading in advance, and the antistatic adhesive resin composition is a method of coextrusion by the methods (2) and (3) above.
  • the pressure-sensitive adhesive film of the present invention can be produced by the following method in addition to the method by coextrusion.
  • thermoplastic polymer composition is formed into a film by a calendering method, a ⁇ die method, an inflation method, etc., and then a support is formed, and then surface treatment is performed as necessary to control the antistatic property.
  • a method of extrusion laminating a fat composition is performed.
  • each molded body (preferably Is a method where the adhesive surface of the support is subjected to surface treatment as necessary and extrusion laminated (dry lamination method).
  • a sheet preferably polyethylene terephthalate coated with an easily peelable compound such as a silicone compound is charged with an organic solvent such as toluene or cyclohexane.
  • an organic solvent such as toluene or cyclohexane.
  • a solution in which the product is dissolved, or a melt-kneaded antistatic adhesive resin composition is applied and dried to obtain a sheet with an antistatic adhesive layer.
  • the antistatic adhesive layer is transferred to the support by pressure-bonding the sheet with the antistatic adhesive layer and a support prepared using the polyolefin resin composition separately.
  • Specific examples of the surface treatment include corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, UV treatment, ion bombardment treatment, and solvent treatment. These may be performed continuously in combination.
  • a primer layer containing a resin component such as polyethyleneimine, polyurethane, and acrylic resin can be formed on the surface of the support before adhesion to the antistatic adhesive layer.
  • the thickness of the primer layer is preferably as it is thinner, for example, 0.1 to: about LO / z m is preferable, and 0.1 to 5 / z m is more preferable.
  • the primer layer can be usually formed by applying a solvent (including water) solution by a known method and drying it.
  • a protective layer is provided on the surface of the antistatic adhesive layer, it may be simultaneously with the formation of the support and the antistatic adhesive layer (may be co-extruded at the same time !,;) Take it at the same time as winding!
  • the antistatic resin composition of the present invention is also suitable for multilayer sheets, multilayer films and the like.
  • a laminate of a sheet (or film) comprising the antistatic resin composition of the present invention; a sheet (or film) also comprising the antistatic resin composition of the present invention; and other materials A two-layer sheet (or a two-layer film) comprising a sheet (or film) that also has a force; two sheets (or films) composed of the antistatic resin composition of the present invention, and disposed therebetween, Examples thereof include a three-layer sheet (or three-layer film) provided with a sheet (or film) that has other material strength.
  • the primer layer in the description of the pressure-sensitive adhesive film of the present invention is disposed between the layers.
  • the antistatic resin composition of the present invention contains 40% by mass or more (preferably 50% by mass or more, more preferably 60% by mass or more) of the above polyolefin resin (A-1), 70 Deformation such as warping and twisting hardly occurs at a temperature of ° C or higher (preferably 80 ° C or higher, more preferably 90 ° C or higher), and a multilayer sheet (multilayer film) can be obtained.
  • a polyolefin resin, a styrene resin or the like alone or a composition containing one or more of these is preferable.
  • the composition contains various fillers, antistatic agents, etc. for the purpose of improving rigidity, heat resistance, etc. and imparting antistatic properties.
  • the thickness of the layer having the antistatic resin composition power of the present invention is preferably 10 for the purpose of stably developing the antistatic property. m or more, more preferably 50 ⁇ m or more, particularly preferably 80 ⁇ m or more.
  • the three-layer type sheet 2 in FIG. 4 includes an intermediate layer 22 having other material strengths, and layers 21a and 21b using the above antistatic resin composition.
  • the method for producing the multilayer sheet is preferably a coextrusion method such as a force T-die method or an inflation method, which can be the same as the method for producing the adhesive film.
  • the sheet and film thus obtained can be further formed into a molded product such as a tray by vacuum forming or the like, if necessary.
  • the antistatic adhesive resin composition of the present invention is also suitable for a double-sided adhesive film or the like.
  • the antistatic adhesive composition of the present invention is formed on both sides of the support composed of the antistatic resin composition of the present invention described in the adhesive film of the present invention.
  • the antistatic adhesive layer made of the antistatic / adhesive resin composition of the present invention is provided on both surfaces of the support made of another material.
  • the thicknesses of the support and the antistatic adhesive layer in this embodiment can be the same as the thicknesses of the support and the antistatic adhesive layer in the description of the adhesive film of the present invention.
  • thermoplastic polymers such as various polyolefin resin compositions, styrene resin compositions, or compositions containing the same.
  • a composition a composition containing the component (A) contained in the above antistatic resin composition is preferable.
  • the composition may contain various additives for the purpose of improving rigidity and heat resistance and imparting antistatic properties.
  • the double-sided pressure-sensitive adhesive film can also be provided with a protective layer on the surface of the antistatic pressure-sensitive adhesive layer for the purpose of protecting the antistatic pressure-sensitive adhesive layer and the like, similarly to the pressure-sensitive adhesive film of the present invention.
  • the constituent material of this protective layer is also as described above.
  • the molded product according to the present invention is a variety of members and parts in the electronic-electric field, the household electrical appliance field, the vehicle field, the sanitary field, the building material field, etc. It is particularly suitable as a member, component, etc. in which static electricity damage is a serious problem.
  • cases such as relay cases, wafer cases, reticle cases, mask cases; trays such as liquid crystal trays, chip trays, memory trays, CCD trays, IC trays; carrier types such as IC carriers; polarizing films; Sheets such as protective sheets of sheets; bobbins of sheets' films; surface protection films such as liquid crystal display devices, light guide plates, plasma displays, polarizing plates, semiconductor-related protective films, protective films in clean rooms, etc. Films; Sheets used in clean rooms; Antistatic bags; Useful for internal parts of equipment such as vending machines.
  • Component (C) (bonded styrene content, vinyl bond content, number average molecular weight, and hydrogenation rate of the polymer);
  • Component (D) (physical properties of rubbery polymer, graft ratio, and intrinsic viscosity);
  • the number average particle diameter of the rubbery polymer latex used for forming the component (D) was measured by a light scattering method.
  • the measuring machine used was LPA-3100 manufactured by Otsuka Electronics Co., Ltd., and the Mummland method was used with 70 integration. It was confirmed with an electron microscope that the particle size of the dispersed graft rubber-like polymer particles in component (D) was almost the same as the latitudus particle size.
  • the following surface of the adhesive film was subjected to 5KV electrification using a static horn meter H-0101 manufactured by SHISID ELECTRIC CO., LTD., And the time for the charge to decay to OV was measured. Applied to the electrically styrene-based resin side.
  • Antistatic property-2 Applied to the adhesive side.
  • ⁇ Slightly transparent (printed material is faintly visible when a test piece is placed on the printed material).
  • the surface appearance on both sides of the test piece was visually evaluated according to the following criteria.
  • the antistatic adhesive layer was peeled 90 degrees at a speed of 300 mmZ from a support of a 15 mm wide adhesive film, and the peel strength (unit: g) was measured.
  • a peel strength (unit: g) was measured by performing a 180 ° peel test on the antistatic adhesive layer at a speed of 300 mmZ from a support of an adhesive film having a width of 25 mm.
  • Adhesion between antistatic adhesive layer and triacetyl cellulose (TAC) film was measured by performing a 180 ° peel test on the antistatic adhesive layer at a speed of 300 mmZ from a support of an adhesive film having a width of 25 mm. (7) Adhesion between antistatic adhesive layer and triacetyl cellulose (TAC) film
  • a TAC film with a width of 25 mm was placed on the adhesive surface of the antistatic adhesive layer of the adhesive film, and a 2 kg roller was reciprocated once for pasting. Thereafter, the film was peeled 180 ° at a speed of 300 mmZ, and the peel strength (unit: g) was measured.
  • A3 polyethylene produced using a meta-catalyst catalyst
  • Kernel KF270 (trade name) manufactured by Nippon Polyethylene Co., Ltd. was used.
  • TOPAS6013 (trade name) manufactured by Polyplastics was used.
  • the norbornene unit amount is 75 to 80%, and the glass transition temperature is 140 ° C.
  • TOPAS8007X10 (trade name) manufactured by Polyplastics was used.
  • the norbornene unit content is 65% and the glass transition temperature is 80 ° C.
  • a solution obtained by reacting titanocene dichloride and triethylaluminum in cyclohexane was added to the remaining block copolymer solution, and a hydrogenation reaction was carried out for 40 minutes under a hydrogen pressure of 50 ° C. and 50 kgfZcm 2 .
  • 2,6G tert-butylcatechol was added in an amount of 0.3 part to 100 parts of the block copolymer, and then the solvent was removed to obtain a block copolymer C5.
  • the amount of n-butyllithium used was increased under the conditions of Production Example 1 to obtain a block copolymer C6 having the same structure as the block copolymer C5 and a number average molecular weight of 100,000.
  • the rubber-modified styrene-based resin obtained in Production Example 3 below was used.
  • the graft ratio of this product was 55%, and the intrinsic viscosity [7?] Of the acetone-soluble component was 0.45.
  • E1 50% aqueous solution of tris (trifluoromethanesulfol) methide lithium
  • Sanconol AQ-50T trade name
  • Electrode TS-5 (trade name) manufactured by Kao Corporation with 100% stearyl monoglyceride was used.
  • Examples 1-1 to 1-18 were all excellent in antistatic property, transparency and appearance of the molded product.
  • the content ratio of the component (A), (B) or (C) is outside the scope of the present invention, and any of antistatic properties, transparency, and appearance of the molded product It was inferior.
  • pellet X an antistatic resin composition
  • the pellet X and the component (A3) were co-extruded using a multilayer inflation extruder (a cylinder, die set temperature; 190 ° C.). After forming a film with a thickness of 25 m for both layers and a total thickness of 50 m, the layer with antistatic resin composition strength becomes the surface side.
  • the bag was manufactured as follows. The transparency and the appearance of the molded product were good. Moreover, the surface resistivity was 7 ⁇ 10 6 ⁇ , and the antistatic property was excellent.
  • Example 1-1 60 parts of component (A3) and 26 parts of component (IV) were changed to 86 parts of component (A3).
  • the transparency and the appearance of the molded product were good.
  • the surface resistivity was 1 X 10 7 ⁇ , and the antistatic property was excellent.
  • Experimental Example 1 1 and Experimental Example 1 The film (100 mm ⁇ 100 mm) was observed for smoothness after standing for 1 hour at a temperature of 80 ° C. Experimental example 1 The film of 10 showed a slight wrinkle. The film of Experimental example 1-1 showed almost no change.
  • pellet X obtained above and component (A3) were mixed with a multi-layer inflation extruder (set temperature of cylinder and die: 190 ° C), and antistatic resin composition A three-layer film in which (pellet X) is both surface layers was produced.
  • the thickness of each layer was 15Z20Z15 m.
  • the transparency and the appearance of the molded product were good.
  • the surface resistivity was 7 7 10 6 ⁇ , and the antistatic property was excellent.
  • Examples 2-1 to 2-16 were all excellent in antistatic property, transparency and appearance of the molded product.
  • the content ratio of the component (B) or (C) was outside the scope of the present invention, and the antistatic property, transparency, and appearance of the molded product were inferior.
  • Example 3-1 to 3-17 First, as a composition for forming a support, the above components (A), (B), (C) and (E) were mixed by a Henschel mixer at the blending ratios shown in Tables 6 to 8, Pellets were obtained by melt-kneading using a screw extruder (set temperature of the cylinder: 220 ° C.).
  • composition for forming the antistatic adhesive layer is also prepared by mixing the above components (A), (B), (C) and (E) with a tumbler at the blending ratios shown in Tables 6 to 8. Was obtained.
  • each of the above-mentioned composition for forming the support and the antistatic adhesive layer was coextruded using a multilayer inflation extruder (set temperature of the cylinder; 210 to 240 ° C) to obtain the thickness of the support.
  • An adhesive film having a thickness of 0 m and an antistatic adhesive layer thickness of 20 m was obtained.
  • antistatic property, transparency, appearance of molded product, adhesion between support and antistatic adhesive layer on each surface of support and antistatic adhesive layer, and control of adhesive film Electric adhesion The adhesion between the surface of the layer and the TAC film was evaluated. The results are shown in Tables 6-8.
  • Examples 3-1 to 3-17 all have antistatic properties, transparency, appearance of the molded product, adhesion between the support and the antistatic adhesive layer, and the adhesive film. Excellent adhesion between the antistatic adhesive layer surface and the TAC film.
  • Example 3 Adhesion of 12 The film was slightly warped.
  • the adhesive film of Examples 3 to 13 had no change at all. Since it contains component (A4), it can be seen that it has excellent heat resistance.
  • Each component of the pressure-sensitive adhesive and styrene-based resin was mixed with a Henschel mixer at the blending ratio shown in Table 9, and then melt-kneaded with a twin-screw extruder (cylinder setting temperature 220 ° C.) to form pellets.
  • Styrenic resin produced a 50 m support film by a calendering method. After corona discharge treatment on one side of the film, a polyethyleneimine layer was formed on the corona discharge treatment surface.
  • a pressure-sensitive adhesive layer having a thickness of 20 ⁇ m was formed on the polyethyleneimine layer side of the film by extrusion lamination.
  • the antistatic property, the adhesiveness between the antistatic adhesive layer and the TAC film, and the adhesive strength between the support (styrene-based film layer) and the antistatic adhesive layer were evaluated by the above evaluation method. (Adhesiveness 1) was evaluated. In addition, the transparency and appearance of the film were visually evaluated.
  • the adhesive films of Examples ⁇ 1 to ⁇ -13 of the present invention have excellent antistatic properties and excellent adhesive strength between the support and the adhesive. It is also easy to control the adhesiveness with the TAC film. Furthermore, it is a film with excellent transparency and appearance.
  • Comparative Example ⁇ 1 is an example in which the amount of component (C) used in the present invention is large outside the scope of the invention, and the amount of component (B) used is small outside the scope of the invention, but antistatic properties are manifested. do not do.
  • Comparative Example 2 is an example in which the amount of component (C) used in the present invention is small outside the scope of the invention, and the amount of component (B) used is large outside the scope of the invention, and there is no problem with antistatic properties. The appearance of the film is inferior and not practical.
  • the above components (A), (B), (C) and (E) are used as the composition for forming the first layer and the third layer.
  • the mixture was melt-kneaded using a twin-screw extruder (cylinder set temperature; 220 ° C.) to obtain pellets (antistatic resin composition).
  • pellets for forming the second layer which is an intermediate layer, pellets having polymer strength described in Table 10 were used.
  • Experimental Examples 1-2 to 1-9 are all three-layer sheets in which the first layer and the third layer are formed using the antistatic resin composition of the present invention. Yes, it has excellent antistatic properties on both surfaces, and the second layer (intermediate layer) contains the same component (A) used to form the first and third layers. It was also excellent.
  • the antistatic resin composition of the present invention is excellent in antistatic property and appearance of a molded product, and also excellent in transparency. Therefore, it is useful as a molding material for molded products such as films and sheets used in fields where static electricity damage is a major problem.
  • the antistatic adhesive resin composition of the present invention is excellent in antistatic properties, transparency and appearance of molded products, molding of molded products such as pressure-sensitive adhesive films and multilayer sheets used in fields where static electricity damage is a major problem. Useful as a material.
  • the molded article such as an adhesive film and multilayer sheet comprising the antistatic resin composition and the antistatic adhesive composition of the present invention is excellent in antistatic property and appearance of the molded article, and is transparent depending on the embodiment. Because of its excellent properties, it is useful as a molding material for molded products such as adhesive films and multilayer sheets used in fields where static electricity damage is a major problem.
  • FIG. 1 is a schematic cross-sectional view showing an example of an adhesive film of the present invention.
  • FIG. 2 is a schematic sectional view showing an example of an adhesive film in which a protective layer is disposed on the surface of the antistatic adhesive layer.
  • FIG. 3 is a schematic cross-sectional view showing an example of an adhesive film in which an antistatic adhesive layer and a protective layer are arranged on both sides of a support.
  • FIG. 4 is a schematic sectional view showing an example of a three-layer sheet using the antistatic resin composition of the present invention.
  • Adhesive film 11; Support, 12, 12a and 12b; Antistatic adhesive layer, 13, 13a and 13b; Protective layer, 2; Three-layer sheet, 21a and 21b A layer formed using the antistatic resin composition of the present invention, 22 an intermediate layer.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention a pour objet une matière de moulage qui est excellente en termes de propriétés antistatiques et d'aspect du moulage et de préférence excellente également en termes de transparence et de résistance à la chaleur et qui est utilisable comme matière de moulage pour la couche autocollante et le substrat d'un film autocollant. L'invention concerne une composition de résine antistatique laquelle comprend (A) une résine de polyoléfine, (B) un copolymère en blocs comprenant un bloc de polymère d'une oléfine et un bloc de polymère hydrophile et (C) au moins un polymère sélectionné dans le groupe constitué de polymères contenant des unités d'un composé diénique conjugué et de produits d'hydrogénation des polymères. On peut contrôler le caractère poisseux en ajustant la quantité de l'ingrédient (A) à incorporer. Lorsque l'ingrédient (A) comprend une résine de polyoléfine contenant des unités cyclooléfines et ayant une température de transition vitreuse de 60-200°C, la résistance à la chaleur est améliorée. Les exemples préférés de l'ingrédient (C) comprennent un copolymère en blocs comprenant un bloc de polymère d'un composé diénique conjugué et un bloc de polymère d'un composé vinylique aromatique et un produit d'hydrogénation de ce copolymère en blocs.
PCT/JP2006/306254 2005-03-29 2006-03-28 Composition de résine antistatique, composition de résine antistatique/autocollante, film autocollant et procédé servant à produire ceux-ci WO2006104133A1 (fr)

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KR1020077022040A KR101243090B1 (ko) 2005-03-29 2006-03-28 제전성 수지 조성물, 제전·점착성 수지 조성물, 점착 필름및 그 제조 방법
CN2006800144143A CN101166784B (zh) 2005-03-29 2006-03-28 抗静电树脂组合物、抗静电/压敏粘合性树脂组合物、压敏粘合膜和它们的制备方法

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EP2093268A1 (fr) * 2006-12-18 2009-08-26 Nitto Denko Corporation Feuille adhésive sensible à la pression
EP2535387A1 (fr) * 2011-06-17 2012-12-19 Nitto Denko Corporation Feuille adhésive sensible à la pression avec propriétés antistatiques
CN103374312A (zh) * 2012-04-23 2013-10-30 泰州现代塑料有限公司 一种用于超高分子量聚乙烯复合材料的聚烯烃粘接树脂
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JP6063737B2 (ja) * 2012-03-12 2017-01-18 東京応化工業株式会社 接着剤組成物、接着フィルムおよび基板の処理方法
US10633465B2 (en) * 2016-03-24 2020-04-28 Kraton Polymers U.S. Llc Block copolymers having semi-crystalline blocks and compositions and articles made therefrom
WO2021070633A1 (fr) * 2019-10-09 2021-04-15 テクノＵｍｇ株式会社 Composition de résine thermoplastique et article moulé de celle-ci
CN112322233A (zh) * 2020-11-23 2021-02-05 广东能辉新材料科技有限公司 含改性sis热塑性弹性体的热熔压敏胶及其制备方法
KR102477947B1 (ko) * 2020-12-29 2022-12-15 한국신발피혁연구원 정전기 흡수용 스펀지 조성물
CN116615493A (zh) * 2021-08-05 2023-08-18 旭化成株式会社 天线部件
CN113789003B (zh) * 2021-11-17 2022-02-25 江苏凯伦建材股份有限公司 一种自清洁抗渗防水片材及其制备方法和应用
CN115627033B (zh) * 2022-10-14 2024-04-16 上海金发科技发展有限公司 一种聚丙烯组合物及其制备方法和应用
CN115895136B (zh) * 2022-11-22 2023-08-29 东藤（上海）新材料有限公司 一种芯片托盘吸塑件及其制备方法

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EP2093268A4 (fr) * 2006-12-18 2012-06-13 Nitto Denko Corp Feuille adhésive sensible à la pression
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EP2535387A1 (fr) * 2011-06-17 2012-12-19 Nitto Denko Corporation Feuille adhésive sensible à la pression avec propriétés antistatiques
CN103374312A (zh) * 2012-04-23 2013-10-30 泰州现代塑料有限公司 一种用于超高分子量聚乙烯复合材料的聚烯烃粘接树脂
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KR101243090B1 (ko) 2013-03-13
CN101875824A (zh) 2010-11-03

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