WO2006104133A1

WO2006104133A1 - Antistatic resin composition, antistatic/pressure-sensitive-adhesive resin composition, pressure-sensitive adhesive film, and process for producing the same

Info

Publication number: WO2006104133A1
Application number: PCT/JP2006/306254
Authority: WO
Inventors: Masaaki Mawatari; Tetsuya Kubota
Original assignee: Techno Polymer Co., Ltd.
Priority date: 2005-03-29
Filing date: 2006-03-28
Publication date: 2006-10-05
Also published as: CN101166784B; KR101243090B1; CN101166784A; CN101875824A; KR20080002777A; CN101875824B

Abstract

[PROBLEMS] To provide a molding material which is excellent in antistatic properties and molding appearance and preferably excellent also in transparency and heat resistance and is usable as a molding material for the pressure-sensitive adhesive layer and substrate of a pressure-sensitive adhesive film. [MEANS FOR SOLVING PROBLEMS] An antistatic resin composition which comprises (A) a polyolefin resin, (B) a block copolymer comprising an olefin polymer block and a hydrophilic polymer block, and (C) at least one polymer selected from the group consisting of polymers containing conjugated diene compound units and products of hydrogenation of the polymers. Tackiness can be controlled by regulating the amount of the ingredient (A) to be incorporated. When the ingredient (A) comprises a polyolefin resin containing cycloolefin units and having a glass transition temperature of 60-200°C, heat resistance is improved. Preferred examples of the ingredient (C) are a block copolymer comprising a polymer block of a conjugated diene compound and a polymer block of an aromatic vinyl compound and a product of hydrogenation of this block copolymer.

Description

Specification

Antistatic resin composition, antistatic / adhesive resin composition, adhesive film, and method for producing the same

Technical field

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.

Background art

[0002] 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. In the latter case, the release paper is removed and the adhesive layer is attached to the adherend during use. When the adhesive film is used for protecting the surface of the adherend, 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. There was a problem that handling, that is, workability was lowered, and 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. As 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.

As means for solving the above problems, 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. However, there has been a problem that static electricity is generated due to a support that is not sufficiently effective in preventing peeling electrification. 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.

[0003] Further, 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. However, 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. There is disclosed 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. However, 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. In addition, 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.

[0004] 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

Problems to be solved by the invention

As described above in detail, in the adhesive film, it is desired to improve the antistatic property for both the adhesive layer and the support.

Depending on the intended use of the adhesive film or sheet, properties such as transparency and heat resistance may be further required. With regard to heat resistance, for example, when printing on the support side of an adhesive film, a material that can withstand temperatures of 80 ° C or higher is required for drying after printing. Therefore, it is required that deformation such as warping and curling does not occur. In addition, any molded product must have at least a practically acceptable appearance.

[0006] 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.

Means for solving the problem

[0007] As a result of intensive studies to achieve the above object, the present inventors have found that a composition containing a predetermined amount of a polyolefin resin, a specific block copolymer, and a specific conjugation polymer.

It was found that the antistatic property and transparency were excellent. In addition, a composition comprising a predetermined amount of these components has been found to be more excellent in tackiness, and in particular, the adhesive strength can be easily controlled by selecting the type and blending amount of the polyolefin resin. all right. Furthermore, By forming a pressure-sensitive adhesive layer using the above-mentioned pressure-sensitive adhesive composition on the surface of a support made of an appropriate resin composition, the adhesion between the support and the pressure-sensitive adhesive layer is excellent, and further transparency is excellent. It was found that an antistatic adhesive film can be obtained.

Furthermore, as a result of intensive studies to achieve the above object, 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.

[0008] Forcibly, according to one aspect of the present invention,

(A) Polyolefin resin (except for the following component (B)) 30 to 95% by mass,

(B) 5-20% by mass of a block copolymer containing an olefin polymer block and a hydrophilic polymer block;

(C) 0-50% by mass of at least one polymer selected from the group consisting of a polymer containing a conjugated diene compound unit and a hydrogenated product thereof;

(However, the total of the component (A), the component (B) and the component (C) is 100% by mass).

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.

[0009] According to another aspect of the invention,

(A) Polyolefin resin (except for the following component (B)) 0 to 59% by mass,

(B) 3 to 60% by mass of a block copolymer containing an olefin polymer block and a hydrophilic polymer block;

(C) 35 to 97% by mass of at least one polymer selected from the group consisting of a polymer containing a conjugated diene compound unit and a hydrogenated product thereof,

(However, the total of the component (A), the component (B) and the component (C) is 100% by mass).) 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.

[0010] According to a first preferred embodiment of the 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.

[0011] According to a second preferred embodiment of the antistatic 'adhesive rosin composition of the present invention, the component (A) is modified with polyolefin (Α'-1) and Ζ or a functional group. Polyolefin (Α′-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 (Α) 0 An antistatic adhesive resin composition comprising: -59% by mass, the above component (Β) 3-60% by mass, and the above component (C) 40-97% by mass is provided. Here, 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.

[0012] As a result, various laminates can be obtained using the antistatic resin composition of the present invention and the antistatic adhesive resin composition of the present invention.

Examples of preferable laminates according to the present invention include the following forms (1) to (4).

(1) 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.

(2) The pressure-sensitive adhesive film as described in (1) above, wherein the polyolefin resin composition is the antistatic resin composition of the present invention. (3) A support made of a thermoplastic polymer composition, disposed on at least one side of the support, and the antistatic adhesive resin composition of the present invention, preferably the second An antistatic adhesive layer comprising an antistatic adhesive layer comprising an antistatic adhesive resin composition according to an embodiment.

(4) 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.

[0013] In the antistatic resin composition and the antistatic and adhesive resin composition of the present invention, the above-mentioned component (A) is a polyolefin containing a cyclic olefin unit and having a glass transition temperature of 60 to 200 ° C. System resin (A-1) and polyolefin resin without cyclic olefin units (A-2), and the ratio of the two contents ((A-1) Z (A-2)) is 95Z5 ~: When LZ99 (mass ratio), heat resistance is improved.

[0014] In the antistatic resin composition and the antistatic and adhesive resin composition of the present invention, 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.

[0015] 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 invention's effect

[0016] 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. In particular, when the component (A) also has the above polyolefin resin (A-1) and (A-2) strength, a molded product having heat resistance can be obtained.

[0017] Since 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. In particular, when the support film is the antistatic resin composition of the present invention, the adhesive film as a whole is excellent in antistatic properties and has a surface resistivity of 10 ⁹ Ω or less under a predetermined condition. can do.

When the support film is the antistatic resin composition of the present invention, 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.

BEST MODE FOR CARRYING OUT THE INVENTION

[0018] Hereinafter, the present invention will be described in detail. In the present specification, “(co) polymerization” means homopolymerization and copolymerization, and “(meth) acryl” means acryl and cocoon or methacryl,

“(Meth) atalylate” means attalate and cocoon or metatalerate.

[0019] 1. Antistatic resin composition

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 , (Β) a block copolymer containing an olefin polymer block and a hydrophilic polymer block (also referred to as “component (Β)” 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).

[0020] 1 1. Component (A)

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. In the present invention, 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.

As the polyolefin-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.

[0021] As the olefins, 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 particularly preferable.

[0022] As the olefins, cyclic olefins can also be used. Cyclic olefins are usually used in combination with the non-cyclic olefins.

The 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. Preferably, cyclic olefin is a compound having 11 or less carbon atoms.

As the above-mentioned cyclic olefin, 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. Specific examples of 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. 1] Hepto-2-ene, 1-methylbicyclo [2. 2. 1] Hepto-2-ene, 7-methylbicyclo [2. 2. 1] hept-2-ene, tricyclo [4. 3. 0. I ² · ⁵ ] — 3— Decene, 2-Methylenotritricyclo [4. 3. 0. I ² · ⁵ ] — 3 Decene, 5 — Methyloretricyclo [4. 3. 0. I ² · ⁵ ]-3 decene, tricyclo [4. 4. 0. I ² · ⁵ ]-3 undecene. These can be used alone or in combination of two or more.

Incidentally, 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.

In addition, 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.

Cyclohydroindene, methyltetrahydroindene, dicyclopentagen, bicyclo [2. 2. 1] -hepter 2,5 gen, 5-methylene 1-2 norbornene, 5 ethylidene 2 norbornene 5-propylene 2 norbornene, 5 isopropylidene 2 norbornene, 5 cyclohexylidene 2 norbornene, 5 bureau 2 norbornene, and the like. These are one kind alone or two kinds A combination of the above can be used.

[0024] 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) ί, preferably ί 0.00-500g / 10 min, more preferably ί. 01 ~ 500g / 10min, more preferably 0.05 ~: LOOg / 10min, each value is preferred with a molecular weight corresponding to this value.

[0025] Accordingly, among the above components (A), 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. Of these, polyethylene, polypropylene, and propylene / ethylene copolymers are preferred. As 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.

Further, the melting point of the above-mentioned polypropylene or propylene copolymer (such as propylene'a-olefin copolymer) is preferably 40 ° C or higher, and the molecular weight is not particularly limited, but from the viewpoint of moldability. From the above, 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.

[0026] Among the components (A), 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.

[0027] When the antistatic resin composition of the present invention is required to have heat resistance, 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. In the present invention, the polyolefin resin (A-1) and (A-2) are also referred to as the component (A-1) and the component (A-2), respectively.

[0028] 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).

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. For 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.

[0029] 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%. % By weight and component (A-2) 90-10% by weight, more preferably component (A-1) 20-80% by weight and component (A-2) 80-20% by weight, particularly preferably component (A-1) 40-80% by mass and component (A-2) 60-20% by mass. When used in the above ranges, excellent heat resistance and molded product appearance are exhibited.

[0030] In the antistatic resin composition of the present invention, 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.

[0031] 1 2. Component (B)

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. In addition, this component (B) can be used alone or in combination of two or more.

In the component (B), 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. However, ml is an integer of 1 or more, and m2 and m2 ′ are both integers of 2 or more, and may be the same or different. In 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.

(1) (bl -b2)

ml

(2) bl-(b2-bl)

ml

(3) b2- (bl -b2)

ml

(4) (bl) (b2)

(5) bl -bl-(b2-b2-bl -bl)

ml

Of these, the block structures (1), (2) and (3), that is, polymer blocks (bl) and (b 2) It is preferable to arrange alternately repeatedly.

[0033] In addition, 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.

In the block structures (1) to (5), 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.

[0034] 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.

In addition to the above compounds, 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.

[0035] In order to make the bonding form of the polymer blocks (bl) and (b2) an ester bond, an amide bond, an ether bond, a urethane bond or an imide bond, 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.

[0036] 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). [0037] 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. Examples of the polymer include polyether (b2-a), polyether-containing hydrophilic polymer (b2-b), and eron polymer (b2-c).

Examples of the polyether (b2-a) include polyether diol, polyether diamine, and modified products thereof.

Examples of the polyether-containing hydrophilic polymer (b2-b) 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.

These may be linear or branched. Further, the 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.

[0038] The polyether diol in the polyether (b2-a) is represented by the general formula (1):

H- (OA ¹ ) — O— E ¹ — O— (Α′θ) i One represented by H and the general formula (2):

n n '

Η- (ΟΑ ² ) — Ο— Ε ² — Ο— (Α ² 0) Examples include those represented by Η.

In the general formula (1), 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 the divalent hydroxyl group-containing groups. It represents the number of alkylene oxides added per hydroxyl group in the compound. coupling case and is of n (OA ¹⁾ and number of (eight ^1.), which Yogumata be different even identical, they are made up of two or more Okishiarukiren groups The format is block or random or a combination of these Misalignment is acceptable. 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.

[0039] 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.

Examples of the aliphatic dihydric alcohol 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.

Examples of alicyclic dihydric alcohols include 1,2- and 1,3-cyclopentanediol, 1,2-, 1,3 and 1,4-cyclohexanediol, and 1,4-cyclohexane. Examples include dimethanol.

Examples of the aromatic dihydric alcohol 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.

Examples of bisphenol 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.

Furthermore, examples of the tertiary amino group-containing diol include N alkyl dialkylanolamines having 1 to 8 carbon atoms.

In the general formula (2), 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.

2 X

In general formula (4), 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 An alkylene group. 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 and are preferably integers of 1 300, more preferably 2 250, especially 10 to: L00. M may be the same as or different from m.

[0041] 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. Examples of the alkylene oxide 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. When two or more alkylene oxides are used in combination, the bond type may be random and Ζ 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.

[0042] Preferable methods for producing the polyether diol represented by the general formula (2) include the following methods (1) and (II).

[0043] (I) Using the above divalent hydroxyl group-containing compound as a starting material, the compound represented by the general formula (5)

[Chemical 5]

CH ₂ — CH— CH ₂ — 0- (A ⁴ 0) _p — R ¹ · '(5)

O

(In formula (5), 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. )

A method of polymerizing glycidyl ether represented by the formula (1) or copolymerizing with an alkylene oxide having 2 to 4 carbon atoms.

[0044] (i) A method in which the above divalent hydroxyl group-containing compound is used as a starting material and a polyether having a chloromethyl group in the side chain is passed. More specifically, epichlorohydrin, or epichlorohydrin and alkylene oxide are addition-copolymerized to obtain a polyether having a chloromethyl group in the side chain, and then the polyether and a C 2-4 polyether. Alkylene glycol and (R ¹ is as described above, X is Cl, Br or I) are reacted in the presence of an alkali, or the polyether and a polyalkylene glycol monocarbyl ether having 2 to 4 carbon atoms are present in the presence of alkali. How to react with.

[0045] As the alkylene oxide having 2 to 4 carbon atoms used here, all of those described above can be used.

[0046] As 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.

[0047] For the purpose of further improving the antistatic property which is the object of the present invention, the component) contains at least one salt (H) selected from the group consisting of alkali metals and alkaline earth metals. be able to. These components can be contained before polymerization of component (B), during polymerization of component (B), or after polymerization of component (B). In addition, 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.

[0048] Specific preferred examples of 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; octyl phenyl sulfonic acid, dodecyl phenyl sulfonic acid, dibutyl phenol sulfo Alkali metal salts of alkylbenzene sulfonic acids having 6 to 18 carbon atoms in the alkyl group, such as acids and dinoylphenol sulfonic acids; alkyl groups such as dimethyl naphthyl sulfonic acid, diisopropyl naphthyl sulfonic acid and dibutyl naphthyl sulfonic acid Alkali metal salts of alkyl naphthalene sulfonic acids having 2 to 18 carbon atoms; alkali metal salts such as fluorinated sulfonic acids such as trifluoromethane sulfonic acid, etc., which are used alone or in combination of two or more Can be used in combination. The component (H) can be used in an amount of preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the component (B) of the present invention.

[0049] In the component (B) according to the present invention, 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).

The 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%.

When the component (B) force S block structure (2) or (3) is provided, 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. For example, 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.

[0050] In addition, the ability to use a known polymerization catalyst in the polymerization reaction is preferable. 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.

[0051] Commercially available products can be used as the component). For example, 300, 303, 230 isotonic force of “Pelestat series” manufactured by Sanyo Kasei Co., Ltd. is suitable.

[0052] In the antistatic resin composition of the present invention, 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.

[0053] 1 3. Ingredient (C)

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.

[0054] 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.

[0055] Further, 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 α-methylstyrene being preferred.

[0056] When the polymer (C1) contains a conjugation compound unit and an aromatic bur compound unit, 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. In addition, 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%.

[0057] When 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.

[0058] 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.

[0059] When 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.

[0060] 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.

In the case where the polymer block (c2) force conjugation compound unit is included, it may have a bull bond.

[0061] 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. In addition, 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.

[0062] The polymer (C1) is known in the technical field of anion polymerization. For example, JP-B 47-28915, JP-B 47-3252, JP-B 48-2423 This is disclosed in Japanese Patent Publication No. 48-20038. Also, the weight with taper block A method for producing a coalescence is disclosed in JP-A-60-81217 and the like.

[0063] Adjustment of the amount of bull bonds (1, 2 and 3, 4-bond content) contained in the polymer block (C1) is N, N, Ν ', Ν, -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.

After obtaining a polymer by the above method, 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.

[0064] 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 <ί 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.

[0065] Preferred examples of the block copolymer as the polymer (C1) include polymers having structures represented by the following formulas (IV) to (XI).

(C ¹ C ² ) (IV)

y

(c ¹ C ² ) -X (V)

y

(C ² — C ¹ ) -C ² (VI)

z

(C ² — C ¹¹ C ¹² ) (VII)

y

(c -c ¹² ) (VIII)

z

(c -c ¹² ) z -x (IX) (c ¹² c ¹¹ c ¹² ), (X)

z,

(c ¹² c ¹¹ c ¹² ), X (XI)

z,

[In each formula, 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, and z 'is an integer of 1 to 5. In each formula, when there are a plurality of C ^{1 s} , they may be the same or different. C ² is the same. ]

[0066] 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. In the above formulas (IV) to (XI), 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.

In the block copolymer preferred as the polymer (C1), the use ratio of the aromatic vinyl compound and the conjugated genie compound is as follows: aromatic vinyl compound conjugated genie compound

~70Ζ30~90 mass ^_0/0 and more preferably the range of the preferred tool 15~65Ζ35~85 mass ^_0/0, and particularly preferably from 20~60Ζ40~80 mass ^_0/0.

Among the above 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.

[0067] As the 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).

On the other hand, the polymer (C2) is a hydrogenated product of the polymer (C1). That is, the polymer

(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

50-: L00%, particularly preferably 90-: L00%.

[0069] As the 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

0 to 90% is preferable, and 70 to 85% is particularly preferable! /.

[0070] Hydrogenation to the polymer (C1) is, for example, JP-B-42-8704, JP-B-43.

— 6636, JP-B 63-4841, JP-B 63-5401, JP-A-2-

This can be carried out by known methods disclosed in 133406, JP-A-1-297413, and the like.

[0071] As the polymer (C2), a commercially available product can be used. For example, “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.

[0072] The melt mass flow rate of the component (C) (measured at a temperature of 230 ° C and a load of 2.16 kg according to ASTM D1238) 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.

[0073] As the component (C), the above polymers (C1) and (C2) can be used in combination.

Further, as the component (C), it is preferable to use the polymer (C2) alone and in combination with the polymers (C1) and (C2). Preferred, 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%.

[0074] In the antistatic resin composition of the present invention, 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.

1 4. Other ingredients

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 (ΧΠ),

Component (E3): a boron compound containing a unit represented by the following general formula (ΧΙΠ),

Ingredient (E4): nonionic surfactant.

[Chemical 6]

(Wherein 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.

[Chemical 7]

[0076] The salt (El) having a key moiety having a fluorinated alkylsulfol group (also referred to as "component (El)" in the present invention) is a fluorinated alkylsulfol group. Means a salt composed of a cation moiety having one or more of the above and an appropriate cation moiety. 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.

[0077] 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-. As the cation part, Li

3 3 3 2 2 3 2 3

Alkali metal ions such as +, Na + and K + can be mentioned, and among these, Li + is preferable.

Therefore, as component (E1), 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.

[0079] When the above component (E1) is 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. Other examples of the 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. . When the component (E1) is dissolved, the concentration is preferably in the range of 0.1 to 80% by mass, more preferably 1 to 60% by mass.

[0080] As the component (E1), a commercially available product can be used. For example, in the solution, “Sanconol 0862-20R”, “Sanconol 0862-13T”, “Sanconol 086 2-10—” manufactured by Sanko Chemical Co., Ltd. “Sanconol AQ—50Τ” (above, trade name) can be used. In the master batch, “Sanconol ΤΒΧ-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.

[0081] When component (E1) is used alone as component (Ε), the content of component (Ε) in the antistatic resin composition of the present invention is such that components (A), (Β) 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.

[0082] The polymer (Ε2) (also referred to as “component (Ε2)” 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%. When the proportion of these units is small, sufficient improvement in antistatic properties may be exerted, and physical properties such as strength that may be difficult to decrease may be deteriorated. The above units are at least 2 in the polymer constituting the component (Ε2). More than 1, preferably 3 It is preferable to contain 30 pieces.

In the above general formula (XII), R ⁵ is a hydrocarbon group, preferably an alkylene group having 24 carbon atoms, and particularly preferably an ethylene group.

In the above general formula (XII), R ⁵ ′ is a hydrogen atom, a halogen atom or a hydrocarbon group. Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom. Examples of 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.

[0084] Examples of the alkyl group 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, 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, 2-butyldecyl group Group, 2-hexyloctyl group, 2-hexyldecyl group, 2-octyldecyl group, 2-hexyldecyl group, 2-octyldodecyl group, 2-decyltetradecyl group, 2-dodecylhexadecyl group, 2 —Hexadecyloctadecyl group, 2-tetradecyloctadecyl group, monomethyl branched-isostearyl group, and the like.

[0085] Examples of the alkenyl group 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. Group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tetradecenyl group, and oleyl group.

[0086] As the 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, β-naphthyl group and the like.

[0087] 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.

[0088] 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.

[0089] In the above general formula (XII), 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). . As 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.

[0090] The urethane residue means an atomic group after the isocyanate group in the monoisocyanate has reacted. Examples of 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.

[0091] Examples of the ester group in the hydrocarbon group having an ester residue 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.

[0092] As the ionic hydrophilic group, an alkylsulfonic acid group C H SO M (k is an integer of 2 to 4 k 2k 3

Is a number. ), Sulfate group—SO M, phosphate group—PO M, methylcarboxy

3 3 2

Rate group CH COOM and the like.

2

In each group, M is a hydrogen atom, a metal atom, or ammonia (including quaternary ammonia).

[0093] When 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. Of these, sodium and potassium are preferred.

In addition, when M is ammonia, its forming substances are ammonia, methylamine, dimethylamine, ethylamine, jetylamine, (iso) propylamine, di (iso) propylamine, monoethanolamine, N methylmonoethanolamine. N ethyl etheramine, diethanolamine, triethanolamine, morpholine, monopropanolamine, dipropanolamine, tripropanolamine, 2 amino-2-methyl-1,3-propanediopearl, aminoethylethanolamine, N, N, Ν ', Ν, monotetrakis (2-hydroxypropyl) ethylenediamine, and the like.

In the above general formula (XII), m is a number of 1 or more, preferably 1 to 300, more preferably 1 to 200, and still more preferably 5 to L00.

[0095] The component (Ε2) 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 (Ν3 From the compound (Ν4) 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. In the formation of the compound (Nl), a compound that can be co-condensed with phenol or a phenol having a substituent, for example, resorcin, catechol, hydroquinone, and azole may be used in combination.

Therefore, a polymer obtained by reacting one or more of the compounds (N1) to (N4) can be used as the component (E2).

[0096] Further, in the formation of the above compound (N1), 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. The ability of addition polymerization of alkylene oxides such as styrene oxide, etc. When the (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 — Ο) 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. When the moiety (R ⁵ -O) is a polyalkylene oxide, R ⁵ is preferably an alkylene group having 2 to 4 carbon atoms, particularly preferably an ethylene group. When the (R ⁵ — ⁵ ) moiety is formed by copolymerization of two or more types of alkylene oxides, one of them is preferably ethylene oxide. In this case, m is preferably 1 to 300, more preferably 1 to 200, still more preferably 5 to: L00.

[0097] Further, 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.

As the component (E2), a commercially available product can be used. For example, “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.

[0099] 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.

[0100] The boron compound (E3) (also referred to as "component (E3)" in the present invention) containing the unit represented by the above general o (ΧΙΠ) is preferably represented by 90 to: LOO mass%, more preferably 95-100 mass%, still more preferably 98-: a compound containing LOO mass%.

In addition, component basis

(E3) is preferably a polymer compound containing at least 5 units.

[0101] Examples of the compound containing the unit represented by the general formula (ΧΙΠ) 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.

[Chemical 8]

[Wherein q is 0 or 1 and when q = l, T is-(Τ ¹ )-(-— (where 但¹ and Τ ³ are the same or different from each other, and the total number of carbon atoms having an ether residue is 100 less oxygenated hydrocarbon radical, T ² is

[Chemical 9]

(However, R ⁹ is a hydrocarbon group having 1 to 82 carbon atoms.) Or

[Chemical o 10]

-

One NHI

[However, R ^1U is a hydrocarbon group having 2 to 13 carbon atoms. ), S, t and u are respectively

, 0 or 1. R ⁶ , R ⁷ and R ⁸ are the same or different organic groups, and r is 10 to: L 000. ]

In the above general formula (XIV), 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.

[0103] Examples of the charge transfer-type conjugate include conjugate forces represented by the following chemical formulas (XV) to (XXII). In the following chemical formulas, a terminal carbon atom and oxygen atom are usually bonded to a hydrogen atom or a hydroxyl group, respectively.

[Chemical 11]

[Chemical 12]

[Wherein R ′ is a residue of polybutene having an average degree of polymerization of 20. ]

[Chemical 13]

[Chemical 14]

[Chemical 15] m

urn

SZ90 £ / 900Zd / lDd 9 £ 0I / 900Z OAV

[0104] The polymer charge-transfer conjugate can be produced by the method described in Japanese Patent No. 2573986.

As the component (E3), a commercially available product can be used. For example, “NOI BORON 400N” (trade name) manufactured by Boron International Co., Ltd. is preferable.

[0105] 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.

[0106] 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.

[0107] Examples of the nonionic surfactant (E4) (also referred to as "component (E4)" in the present invention) include esters of polyhydric alcohols, nitrogen-containing compounds, and the like. .

[0108] Examples of the ester of the polyhydric alcohol 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.

Examples of the polyglycerol ester include diglycerol monolaurate, diglycerol monomyristate, diglycerol monopalmitate, diglycerol monostearate, diglycerol monobenzoate, and diglycerol monooleate.

[0109] Examples of 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.

Examples of the propylene glycol ester include propylene glycol monostearate.

Of these, glycerol monostearate, diglycerol monostearate, glycerol monolaurate, diglycerol monolaurate and sorbitan monostearate are preferred.

[0110] Examples of nitrogen-containing compounds include ammine compounds and amido compounds.

Examples of 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.

[0111] The amide compounds include lauryl diethanolamide, myristyl diethanolamide, palmityl diethanolamide, behyl-butanolamide, oleyljetanolamide, lauryl diisopropanolamide, myristyl diisopropanolamide, noremithyl diisopropanolamide. , Stearyl diisopropanolamide, and oleyl diisopropanolamide.

Of these, lauryl diethanolamine and stearyl diamine are preferred for the amine compound. Ethanolamine is particularly preferred.

[0112] 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.

[0113] 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.

[0114] 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. In addition, for the purpose of improving miscibility, a master batch can be used. 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.

[0115] As described above, 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.

[0116] The antistatic resin composition of the present invention further comprises 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.

[0117] In the present invention, 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.

[0118] Examples of the antistatic agent 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.

[0119] Examples of the halide include lithium chloride, sodium chloride salt, potassium salt salt, lithium bromide, sodium bromide, potassium bromide and the like.

Examples of perchlorates include lithium perchlorate, sodium perchlorate, and potassium perchlorate.

Examples of the carboxylate include potassium acetate and lithium stearate.

[0120] Examples of the 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. Preferred are salts of aromatic sulfonic acids having 6 to 18 carbon atoms such as acid and dibutylnaphthyl sulfonic acid.

[0121] The antistatic property-imparting aid can be blended in the production of the antistatic oil composition of the present invention. For example, before polymerization of component (B), during polymerization of component (B), and component It can be blended at any time after the polymerization of (B). 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.

[0122] The processing aid is not particularly limited as long as it does not impair transparency and antistatic properties. For example, 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. .

[0123] 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.

[0124] As 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. Examples of 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. [0125] As 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.

[0126] In order to obtain the required performance, 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.

As the thermoplastic resin, polyamide resin; polyester resin 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. Examples of thermoplastic elastomers include polyamide elastomers and polyester elastomers.

Furthermore, examples of thermosetting resin include epoxy resin, phenol resin, urea resin, and the like.

[0127] 1 5. Manufacturing method and molded product

In the antistatic resin composition of the present invention, 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. In the case of forming a molded product as it is after kneading, 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.

[0128] 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 Ω or less under conditions of a temperature of 23 ° C and a humidity of 50% RH. It is preferably 9 × 10 ¹¹ Ω or less, more preferably 9 × 10 ¹⁰ Ω or less, and particularly preferably 5 × 10 ⁹ Ω or less.

[0129] The shape of the molded product may be in accordance with the purpose, application, etc., such as a sheet, a film, etc. Thin bodies (thickness: LOOmm); rod-like bodies such as round bars and square bars; and further modifications thereof; trays, cases, and the like.

When the molded article is a sheet, the thickness thereof is preferably 0.2 to: LOmm, more preferably 0.5 to 5 mm.

In the case of a film, the thickness is preferably 5 to 200 μm, more preferably 10 to 150 πι.

Note that 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.

[0130] 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.

[0131] 2. Antistatic, adhesive resin composition

The antistatic adhesive composition according to the present invention comprises 0 to 59% by mass of the above-described component (Α) polyolefin-based resin (excluding the following component (Β)), and a block of the above component (Β). 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 (Α), component (Β) and component ( The sum of C) is 100% by mass.) The component (Α), component (Β) 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.

[0132] According to a first preferred embodiment of the antistatic 'adhesive resin composition of the present invention, the above components

The contents of (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%. As the component (C) that can be used, “Dynalon 1320P”, “Dynalon 1 321P” (trade name) manufactured by JSR, etc. are preferably used. In addition, 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.

In addition, when there is too much content of the said component (A), adhesiveness may not be enough.

If 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.

If the content of the component (C) is too large, 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.

According to a second preferred embodiment of the antistatic 'adhesive rosin composition of the present invention, the component (A) is modified with polyolefin (Α'-1) and Ζ or a functional group, and the polyolefin (Α '-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 (Α) 0 to 59 mass %, The above component (Β) 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 (Α'-1) and a polyolefin resin modified with a resin or functional group (Α'). — 2) There will be power.

Polyolefin resin (Α'-1) is a modified polyolefin resin, and the content of the polyolefin resin (Α) 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.

[0134] In the antistatic adhesive rubber composition according to the second preferred embodiment, the polyolefin resin (榭 '-1) has a molecular weight sufficient as a molding resin at room temperature. For example, when ethylene is the main component, 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. As the polyethylene used here, any of high density polyethylene, low density polyethylene, and linear low density polyethylene can be used. The above component (Α'-2) is a polyolefin modified with a functional group. It is fat. Preferably, 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 <ί 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).

[0135] 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.

Examples of the unsaturated acid used here 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.

[0136] 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 (Α′-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.

[0137] The above component (Α'-1) is used for the purpose of adjusting the tackiness of the pressure-sensitive adhesive. On the other hand, the above component (Α'-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. .

In the antistatic adhesive rubber composition according to the second preferred embodiment, the amount of the component (Α) used is 100 mass in total of the components (Α) and (Β) 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. In order to enhance the use effect of the component (A'-2), the preferred amounts of the component (Α'-1) and the component (Α'-2) are both (Α 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). If the above component (Α'-1) is less than the above range, the adhesive adjustment function is poor, and if it exceeds the range, the stickiness is poor. On the other hand, if the component (Α′-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.

[0138] In the antistatic adhesive resin composition according to the second preferred embodiment, the component (Β) 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. In the antistatic adhesive rubber composition according to the second preferred embodiment, the above components (

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. In the case of containing component (A), 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.

[0139] In a second preferred embodiment of the antistatic adhesive resin composition of the present invention, 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.

In 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.

When the antistatic adhesive resin composition of the second preferred embodiment is used as an adhesive used as a protective film for a display device, 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.

[0140] In the component (C) of the antistatic 'adhesive resin composition of the second preferred embodiment, the use ratio of the aromatic vinyl compound and the conjugated gen compound is: aromatic vinyl compound Z conjugated gen compound = The range of 5 to 70 Z is preferably 30 to 95% by mass, more preferably 10 to 65% 35 to 90% by mass, and particularly preferably 15 to 60% 40 to 85% by mass. 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%.

[0141] In the antistatic adhesive rubber composition of this second preferred embodiment, 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.

[0142] 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. In addition, 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.

[0143] 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. In the case of forming a molded product as it is after kneading, 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.

[0144] 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 Ω. Or less, more preferably 9 × 10 ¹¹ Ω or less, further preferably 9 × 10 ¹⁰ Ω or less, particularly preferably 5 × 10 ⁹ Ω or less It can be.

[0145] 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. When the molded article is a sheet, the thickness thereof is preferably 0.2 to: LOmm, more preferably 0.5 to 5 mm.

[0146] 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.

[0147] 3. Adhesive film

3- 1. Composition of adhesive film

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.

Therefore, according to the present invention, there is provided 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.

The 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.

Examples of 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.

[0148] 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. Further, 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.

[0149] 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. .

[0150] 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 α-olefins, and a copolymer of α-olefin and other bur monomers. Specifically, low density polyethylene (LDPE), medium density polyethylene, high density polyethylene (HDPE), ultra high molecular weight polyethylene (UHMPE); 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 α-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; polymethylpentene (ΜΡΧ); ethylene and butyl acetate Copolymers with beryl monomers such as ethyl acrylate, methacrylate, ethyl methacrylate, maleic acid, maleic anhydride; copolymers of polyethylene or ethylene and a-olefin are used as acrylic acid, maleic acid And a copolymer modified with an unsaturated carboxylic acid such as a derivative thereof, etc. Furthermore, the component (B) contained in the antistatic resin composition of the present invention can also be used. Can be used singly or in combination of two or more.

Therefore, only 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. In the latter case, the antistatic property of the support and the antistatic property as an adhesive film are excellent.

Among these, 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. As the propylene / ethylene copolymer, 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. In particular, when 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. Examples of 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. These can be used alone or in combination of two or more. Preferable are polybutadiene, butadiene'styrene copolymer and its hydrogenated product, ethylene'propylene copolymer, ethylene'propylene'non-conjugated gen copolymer, acrylic rubber, and silicone rubber. Particularly preferred are polybutadiene and butadiene'styrene copolymers. The butadiene 'styrene copolymer used here is usually a block. And z or random copolymers are used. As the styrene-based resin, those containing a rubbery polymer having a flexible surface when used as a support film are preferable.

[0153] rubbery polymer content in the styrene-based榭脂is a styrene榭脂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.

In addition, the said gel content rate can be calculated | required by the method shown below. That is, the rubber polymer lg was put into 100 ml of toluene and allowed to stand at room temperature for 48 hours, and then the toluene insoluble matter and the wire mesh filtered through a 100 mesh wire mesh (with a mass of W1 gram) were heated at 80 ° C for 6 hours. Vacuum dry, weigh (weight is W2 grams), and calculate by the following formula (1).

[0154] 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.

[0155] Examples of the aromatic vinyl compound constituting the vinyl monomer used in the styrene-based resin include styrene, α-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 α-methylstyrene are preferred.

Other 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. As 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. In addition, if necessary, at least one of various other functional group-containing compounds is used in combination. Other 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.

[0156] Examples of cyanobi-louis compounds used here include acrylonitrile, methacrylonitrile, etc., and these can be used alone or in combination of two or more. . When a cyan compound is used, chemical resistance can be imparted. When a cyan compound is used, the amount used is preferably 1 to 60% by mass, more preferably 5 to 50% by mass in the monomer component.

Examples of (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.

Examples of maleimide compounds include maleimide, Ν-maleimide, Ν-cyclohexylmaleimide, and the like. These may be used alone or in combination of two or more. In order to introduce a maleimide unit, maleic anhydride may be copolymerized and subsequently imidized. When a maleimide compound is used, heat resistance is imparted. When a maleimide compound is used, the amount used is preferably 1 to 60% by mass, more preferably 5 to 50% by mass in the monomer component.

[0157] Examples of 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.

Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and the like. These may be used alone or in combination of two or more.

Examples of hydroxyl-containing unsaturated compounds 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.

[0158] 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.

Examples of the oxazoline group-containing unsaturated compound include bruoxazoline, and these can be used alone or in combination of two or more.

Examples of 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.

[0159] 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. Among 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. On the other hand, 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. .

[0160] 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.

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.

Further, it is preferable to use redox systems such as various reducing agents, sugar-containing iron pyrophosphate formulations, sulfoxylate formulations, etc. as polymerization initiation aids.

Examples of the chain transfer agent include octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-xyl mercaptan, terpinolene and the like.

Examples of the emulsifier 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. A rosinate such as potassium rosinate can be used.

[0161] Incidentally, in the emulsion polymerization, 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. At this time, two or more kinds of latexes obtained by emulsion polymerization may be appropriately blended and then coagulated. As the 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.

[0162] 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

, Dimethylformamide, N-methylpyrrolidone and the like.

The polymerization temperature is preferably in the range of 80 140 ° C, more preferably 85 120 ° C. In the polymerization, 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, Γ-azobis (cyclohexane-1—power (Both-tolyl) and the like are preferably used. When a chain transfer agent is used, for example, mercaptans, terpinolenes, OC-methylstyrene dimer, etc. can be used.

In the case of production by bulk polymerization or suspension polymerization, 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.

[0163] Further, 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 | required by following formula (2).

[0164] Graft ratio (mass ^{_{0/0) = {(T-}} S) / S} X 100 · ·· (2)

In the above formula (2), 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 mass (g) of insoluble matter obtained by centrifuging for 60 minutes in a centrifuge (rotation speed: 23, OOOrpm) and separating the insoluble matter and the soluble matter, and S is the component (D) lg Is the mass (g) of the rubbery polymer contained in.

[0165] In addition, the intrinsic viscosity [η] (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 ΟΟθΑ. The average particle diameter can be measured by a known method using an electron microscope.

[0166] 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. As a preferable antistatic agent, an antistatic agent (F) having the above-mentioned component (B) and a block copolymer having a polyamide block (F-2-1) and a hydrophilic polymer block (F-2-2) shown below (F ). Particularly preferred is the antistatic agent (F) shown below.

[0167] 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 ring-opening polymerization of Ratatamu such as lauryl rata Tam, .omega. § Minokapuron acid, _omega - Aminoena Acid, aminoundecanoic acid, 1, 2-amino-dodecanoic acid and amino acids forces polyamides derived, as well has these copolymerized polyamides, further to include mixtures polyamides.

[0168] As the 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.

(i) A method in which a polyamide is polymerized, a dicarboxylic acid compound is added, the both ends of the polyamide component are carboxylated, and poly (alkylene oxide) glycol is added and polymerized to obtain a polyether polyamide.

(ii) Dicarboxylic acid so that both ends of the molecule are substantially carboxylated during polyamide polymerization. A method of obtaining a polyether polyamide by polymerizing an excessive addition of an acid compound and further polymerizing a poly (alkylene oxide) glycol.

(iii) A method for obtaining a polyether polyamide by batch polymerization of a polyamide-forming component and an excessive amount of a dicarboxylic acid compound and poly (alkyleneoxide) diol in a specified amount.

In the above method, a particularly preferable method is the method (i).

In addition, alkali metal and Z or alkaline earth metal salts (H) described in the explanation of the polymer block (b2) can be used.

[0169] 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.

In the above antistatic agent (F), 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.

Further, the 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.

[0170] Each composition of the thermoplastic polymer can be obtained by various extruders, Banbury mixers, aders, continuous-kinders, rolls, and the like.

When manufacturing a base film using a support that also has thermoplastic polymer strength, 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.

[0171] The above 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.

[0172] 3- 2. Preferred embodiment of adhesive film

In the first embodiment of 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. 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).

In the case of the second embodiment of the antistatic adhesive resin composition of the present invention, it is preferable to use a styrene resin as the 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. A mode (ii) to be provided, and a support (hereinafter referred to as a polyolefin-based resin composition) containing either one of the components (A) and (B) and components other than these components (A) and (B) , “Support (3)”) and an antistatic adhesive layer [iiij force S.

[0173] As a specific example of the 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)!ゝ Composition; contains component (B) and component (C) and does not contain component (A)! ヽ 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.

[0174] The supports (2) and (3) may contain an additive additive that can be blended in the antistatic resin composition of the present invention. In the case of the support (2), the content of the additive is that of the present invention. The description in the antistatic oil-absorbing composition can be applied. In the case of the support (3), 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.

In particular, when the adhesive film is required to have antistatic properties, the antistatic resin composition of the present invention (the above embodiment [ii]) is preferable. In addition, when heat resistance is required, 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 μm.

On each surface of the support, 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 μm, more preferably 5 to 50 μm. In addition, 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.

[0175] 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. With regard to the adhesive property with excellent antistatic properties, 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.

For antistatic properties (surface resistivity under conditions of temperature 23 ° C and humidity 50% RH), preferably 5 X 10 ¹² Ω or less, more preferably 9 X 10 ¹¹ Ω or less, depending on the support surface. More preferably, it is 9 × 10 ¹⁰ Ω or less, and particularly preferably 5 × 10 ⁹ Ω or less.

[0176] 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. 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.

[0177] The pressure-sensitive adhesive film of the present invention will be described with reference to the drawings.

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. Protective layers 13a and 13b.

[0178] 3- 3. Manufacturing method of adhesive film

The pressure-sensitive adhesive film can be produced by a known method, and the production method is not particularly limited.

However, in the present invention, a 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.

[0179] In the step of obtaining the adhesive film by coextrusion, (1) a thermoplastic polymer composition and an antistatic adhesive composition obtained by previously melt-kneading the adhesive resin composition by the above method may be used (2) Thermoplastic polymer composition and antistatic 'A mixture of the components of the adhesive resin composition may be melt kneaded at the time of coextrusion. (3) 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. As said 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.

[0180] The pressure-sensitive adhesive film of the present invention can be produced by the following method in addition to the method by coextrusion.

(1) First, a thermoplastic polymer composition is formed into a film by a calendering method, a τ 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.

(2) After separately producing a support and an antistatic adhesive layer (film or sheet) using a thermoplastic polymer composition and an antistatic adhesive adhesive composition, 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).

(3) First, 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. 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. Thereafter, 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.

[0181] 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.

Furthermore, 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. Further, the primer layer can be usually formed by applying a solvent (including water) solution by a known method and drying it.

[0182] When 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!

[0183] 4. Multilayer sheet (Multilayer film) The antistatic resin composition of the present invention is also suitable for multilayer sheets, multilayer films and the like. As an aspect thereof, 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. In addition, the primer layer in the description of the pressure-sensitive adhesive film of the present invention is disposed between the layers.

When 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.

[0184] As other materials, a polyolefin resin, a styrene resin or the like alone or a composition containing one or more of these is preferable. In particular, it is preferable to use the component (A) contained in the antistatic resin composition of the present invention alone or a composition containing the component (A). The composition contains various fillers, antistatic agents, etc. for the purpose of improving rigidity, heat resistance, etc. and imparting antistatic properties.

[0185] In the multilayer sheet (multilayer film), 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 μm or more, particularly preferably 80 μm or more.

[0186] As the multilayer sheet, a three-layer sheet will be described with reference to the drawings.

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.

[0187] The method for producing the multilayer sheet (multilayer film) 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.

[0188] 5. Double-sided adhesive film The antistatic adhesive resin composition of the present invention is also suitable for a double-sided adhesive film or the like. As for the mode, 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. In addition to the aspect provided with the antistatic adhesive layer, 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.

[0189] In addition to the antistatic resin composition of the present invention, other materials include thermoplastic polymers such as various polyolefin resin compositions, styrene resin compositions, or compositions containing the same. A composition. In particular, 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.

[0190] 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.

[0191] The molded product according to the present invention, that is, the molded product having the above-described antistatic resin composition strength, 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. Specifically, 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.

Example

[0192] The ability to explain the present invention in more detail with reference to the following examples, the present invention is not limited to the powerful examples as long as it does not exceed the gist of the present invention. % Is based on mass unless otherwise specified.

[0193] 1. Evaluation method

The measuring method of each evaluation item in the following examples and comparative examples is shown below.

[0194] (1) Component (C) (bonded styrene content, vinyl bond content, number average molecular weight, and hydrogenation rate of the polymer);

(1 1 1) Amount of bound styrene;

It was measured on the polymer before hydrogenation. Calibration curve force by the infrared method based on the absorption of the phenyl groups of the 699cm ^_1 was also determined.

(1 1 2) number average molecular weight;

It was measured on the polymer before hydrogenation. Obtained from gel permeation chromatography (GPC).

(1-3) Vinyl bond amount;

Measured with the polymer before hydrogenation. Obtained by infrared method (Morello method).

(1 4) Hydrogenation rate;

Measurements were taken on the polymer after hydrogenation. Calculated from the spectrum reduction of unsaturated double bonds in 100MH ¹ H-NMR ^ vector measured at 15% concentration using tetrasalt ethylene as solvent.

z

I put it out.

[0195] (2) Component (D) (physical properties of rubbery polymer, graft ratio, and intrinsic viscosity);

(2-1) Gel content of rubbery polymer: according to the above method.

(2-2) Number average particle diameter of rubbery polymer latex;

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.

(2-3) Graft ratio of component (D): According to the method described above.

(2 4) Intrinsic viscosity [7?] Of component (D);

[0196] (3) Antistatic

(3-1) Surface resistivity The specimen is left for 48 hours under conditions of a temperature of 23 ° C and a humidity of 50% RH, and then the surface resistivity (Ω) is measured with a resistivity meter (trade name “Hirester UP MCP-HT450”, Mitsubishi Chemical Corporation). Measured at an applied voltage of 500V.

(3-2) Antistatic measurement

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.

(4) Transparency

Evaluation was made according to the following criteria.

○ (or “transparent”); there is a clear feeling (when the test piece is placed on the printed matter, the printed matter can be seen through).

Δ: Slightly transparent (printed material is faintly visible when a test piece is placed on the printed material).

X: Opaque (when the test piece is placed on the printed material, the printed material cannot be read).

(5) Molded product appearance

The surface appearance on both sides of the test piece was visually evaluated according to the following criteria.

◯ (or “good”): excellent in smoothness and good.

Δ: There is a part inferior in smoothness.

X (or “bad”); smooth ¾ ^ poor and bad.

(6) Adhesiveness between support and antistatic adhesive layer

(6— 1) Adhesiveness 1

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.

(6-2) Adhesiveness 1

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. (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.

2. Antistatic resin composition and antistatic material component

2— 1. Component (A)

(1) A1 (Homo type polypropylene)

“NOVATEC pp MG2TJ (trade name) manufactured by Nippon Polypro Co., Ltd. was used.

(2) A2 (Random type polypropylene)

“NOVATEC pp EG7F” (trade name) manufactured by Nippon Polypro was used.

(3) A3 (polyethylene produced using a meta-catalyst catalyst)

“Kernel KF270” (trade name) manufactured by Nippon Polyethylene Co., Ltd. was used.

(4) A4 (ethylene norbornene copolymer)

“TOPAS6013” (trade name) manufactured by Polyplastics was used. The norbornene unit amount is 75 to 80%, and the glass transition temperature is 140 ° C.

(5) A5 (Homo type polypropylene)

“NOVATEC pp FY6CJ (trade name) manufactured by Nippon Polypro Co., Ltd. was used.

(6) A6 (low density polyethylene)

“NOVATEC LL UF422” (trade name) manufactured by Nippon Polyethylene Co., Ltd. was used.

(7) A7 (low density polyethylene)

“NOVATEC LD LF122J (trade name) manufactured by Nippon Polyethylene Co., Ltd. was used.

(8) A8 (maleic anhydride modified polyethylene)

“Yumettas 2000” (trade name) manufactured by Sanyo Chemical Industries, Ltd. was used.

(9) A9 (ethylene 'norbornene copolymer)

“TOPAS8007X10” (trade name) manufactured by Polyplastics was used. The norbornene unit content is 65% and the glass transition temperature is 80 ° C.

(10) A10 (Gas phase process meta-polycene polyethylene)

“Nomolex NF464N” (trade name) manufactured by Nippon Polyethylene Co., Ltd. was used. [0199] 2- 2. Component (B)

(1) B1 (Polyolefin / Polyether multiblock copolymer)

“Pelestat 230” (trade name) manufactured by Sanyo Chemical Industries, Ltd. was used.

(2) B2 (Polypropylene / polyether multi-block copolymer)

“Pelestat 303” (trade name) manufactured by Sanyo Chemical Industries, Ltd. was used.

[0200] 2- 3. Component (C)

(1) C1 (High vinyl type hydrogenated polymer)

JSR "DYNARON 1321 P" (trade name) was used.

(2) C2 (hydrogenated polymer with polyethylene block)

“DYNARON6200P” (trade name) manufactured by JSR was used.

(3) C3 (High vinyl type hydrogenated polymer)

“DYNARON1320P” (trade name) manufactured by JSR was used.

(4) C4 (Styrene / Butadiene / Styrene Block Copolymer)

JSR “TR2500” (trade name) was used.

[0201] (5) C5 (hydrogenated styrene butadiene block copolymer)

The hydrogenated styrene butadiene block copolymer obtained in Production Example 1 was used. Row 1

The stirrer and the jacketed autoclave were dried and purged with nitrogen, and a solution of cyclohexane and 35 parts of butadiene was added. Subsequently, n-butyllithium was added to carry out isothermal polymerization at 50 ° C. When the addition rate reached 100%, 0.75 parts of tetrahydrofuran, 45 parts of butadiene, and 15 parts of styrene were added, and the temperature rising polymerization was performed at 80 ° C. at 50 ° C. force. When the conversion rate reached 100%, 5 parts of styrene was added, and a polymerization reaction was further performed to obtain an A—B1-B2 triblock copolymer before hydrogenation. A part of the resulting block polymer solution was sampled, 0.3 part of 2,6-di-tert-butylcatechol was added to 100 parts of the block copolymer, and then the solvent was removed by heating. Styrene block 5% (A block), 1,2 Bull content of butadiene part 35%, Styrene styrene content 15% Styrene 'Butadiene block 60% (B1 block), 1,2 Bull content 8% butadiene block 35% (B2 The number average molecular weight was 200,000. 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.

[0202] (6) C6 (hydrogenated styrene butadiene block copolymer)

The hydrogenated styrene butadiene block copolymer obtained in Production Example 2 below was used. Production example 2

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.

[0203] 2-4. Ingredient (D)

(D DI (Rubber-modified styrene-based resin)

The rubber-modified styrene-based resin obtained in Production Example 3 below was used.

Row 3

After replacing the agitator and jacketed autoclave with nitrogen, add 50 parts of polybutadiene latus (average particle size 2,500A) (solid content), 0.5 part of potassium laurate, 120 parts of ion-exchanged water, and start stirring. did. After adding 9.2 parts of methyl methacrylate and 3.3 parts of styrene, the temperature was raised, and when the internal temperature reached 0 ° C, the sulfoxylate-based aqueous starting agent solution and cumene hydride peroxide 0 04 parts were added to initiate the polymerization reaction. 1 hour after the start of polymerization, an emulsion solution consisting of 27.5 parts of methyl methacrylate, 10 parts of styrene, 0.5 part of tert-dodecyl mercaptan, 0.5 part of potassium laurate, and 20 parts of ion-exchanged water, The polymerization reaction was carried out while continuously adding 0.1 part of a tamennoide-mouthed baroxide and an aqueous solution of a sulfoxylate-based starting aid over 4 hours, and then stirring was continued for another 2 hours, followed by 50 ° The polymerization reaction was terminated by cooling to C. The reaction product latex was coagulated with an aqueous sulfuric acid solution, washed with water and then dried to obtain rubber-modified styrene-based resin D1.

The graft ratio of this product was 55%, and the intrinsic viscosity [7?] Of the acetone-soluble component was 0.45.

[0204] (2) D2 (Styrenic resin without rubbery polymer)

The styrene-based resin obtained in Production Example 4 below was used. Production Example 4

After replacing the stirrer and jacketed autoclave with nitrogen, in a nitrogen stream, 73.4 parts of methyl methacrylate, 26.6 parts of styrene, 20 parts of toluene, 0.1 part of tert-dodecyl mercaptan were added and stirred and heated. Started. When the internal temperature reaches 50 ° C, 0.5 part of benzoyl peroxide is added, the temperature is further increased, and after reaching 80 ° C, polymerization is performed while controlling at 80 ° C-constant. It took 1 hour from the 6th hour after the start of the reaction to raise the temperature to 120 ° C, and the reaction was further completed for 2 hours. After cooling to 100 ° C, the reaction mixture is extracted from the autoclave, unreacted substances and solvent are distilled off by steam distillation, pulverized, devolatilized with an extruder equipped with VENT, pelletized, and no rubber polymer is present. Styrene-based resin D2 was obtained. This had an intrinsic viscosity [7?] Of 0.45.

[0205] 2- 5. Ingredients)

(1) E1 (50% aqueous solution of tris (trifluoromethanesulfol) methide lithium) “Sanconol AQ-50T” (trade name) manufactured by Sanko Chemical Industry Co., Ltd. was used.

(2) Ε2 (polymer type antistatic agent)

“Ade force Nord AS-113” (trade name) manufactured by Asahi Denki Kogyo Co., Ltd. with a polymer antistatic agent content of 65% was used.

(3) E3 (polyethylene masterbatch containing 7% organoboron compound)

Boron International Co., Ltd. “NOI BORON MB400N-8LDPE” (trade name) was used.

(4) E4 (Nonionic surfactant)

“Electrostripper TS-5” (trade name) manufactured by Kao Corporation with 100% stearyl monoglyceride was used.

[0206] 2-6. Ingredient (F)

A polyamide-polyether multi-block copolymer “Pelestat N C6321” (trade name) manufactured by Sanyo Chemical Industries, Ltd. was used.

2- 7. Ingredient (G) (Processing aid)

Using Mitsubishi Rayon's ultra-high molecular weight acrylic polymer "Metaprene P531A" (trade name) [0207] 3. Manufacture and evaluation of antistatic resin composition

Examples 1 1 to 1 14 and Comparative Examples 1 1 to 1 5

After mixing the above components (A), (B), (C) and (E) with a Henschel mixer at the blending ratios shown in Tables 1 and 2, a twin-screw extruder (cylinder set temperature; 220 The mixture was melt-kneaded using (C) to obtain pellets (antistatic resin composition).

After the pellets were sufficiently dried, they were molded using an injection molding machine (set temperature of the cylinder; 220 ° C) to obtain a flat plate test piece having a thickness of 1.6 mm. Using this test piece, the antistatic property (surface resistance), transparency and appearance of the molded product were evaluated. The results are shown in Table 1 and Table 2.

[0208] Examples 1 15 to 1 18

After mixing the above components (A), (B), (C) and (E) with a Henschel mixer at the blending ratio shown in Table 3, a twin screw extruder (cylinder set temperature; 220 ° C) Was used for melting and kneading to obtain pellets (antistatic resin composition).

After the pellets have been thoroughly dried, use an inflation extruder (cylinder, die set temperature; 190 ° C for Examples 1-15 and 1-16, 160 ° C for Examples 1-17 and 1-18) Extrusion was carried out to obtain a bag having a film thickness of 50 / zm. Using this film, the antistatic property (surface resistivity), transparency and appearance of the molded product were evaluated. The results are shown in Table 3.

[0209] [Table 1]

^ Table

s¾ Table 2

Table 3

[0212] From Table 1 to Table 3, the following is clear.

Examples 1-1 to 1-18 were all excellent in antistatic property, transparency and appearance of the molded product. On the other hand, in Comparative Examples 1-1 to 1-5, 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.

[0213] 4. Manufacture and evaluation of bags with two-layer structure

Experimental example 1 1

First, 60 parts of the above component (A3), 26 parts of component (A4), 14 parts of component (B2), and 2 parts of component (E1) were mixed with a Henschel mixer, and then a twin screw extruder (cylinder Was then melt-kneaded at 220 ° C. to produce pellet X (an antistatic resin composition), which was sufficiently dried. Thereafter, 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 Ω, and the antistatic property was excellent.

Experimental example 1 10

In 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 Ω, 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.

[0214] 5. Manufacture and evaluation of films with three-layer structure

Example 1 11

Using Experimental Example 1-1, 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 Ω, and the antistatic property was excellent.

Experimental example 1 12

In the production of Pellet X in Experimental Examples 1-11, the production was the same except that 60 parts of component (A3) and 6 parts of component (成分 4) 2 were changed to 86 parts of component (A3). The resulting three-layer film had good transparency and molded product appearance. In addition, the surface resistivity was 1 × 10 ⁷ and the antistatic property was excellent.

The smoothness of the films of Experimental Example 1-11 and Experimental Example 1-12 (100 mm × 100 mm) after standing for 1 hour at a temperature of 80 ° C. was observed. Experimental example 1 The film of 12 showed a force with a slight wrinkle. The film of Experimental example 1-11 had a force with almost no change.

[0215] 6. Manufacturing and evaluation of antistatic adhesive composition

Examples 2-1 to 2-16 and Comparative Example 2-1

After mixing the above components (A), (B), (C) and (E) with a Henschel mixer at the blending ratios shown in Tables 4 and 5, a twin screw extruder (set temperature of the cylinder; 220 ° C) And kneaded to obtain pellets (antistatic adhesive rubber composition).

After the pellets were sufficiently dried, they were molded using an injection molding machine (set temperature of the cylinder; 220 ° C) to obtain a flat plate test piece having a thickness of 1.6 mm. Using this test piece, the antistatic property (surface resistance), transparency and appearance of the molded product were evaluated. The results are shown in Table 4 and Table 5 [Table 4]

Table 4 ^ () (a0217

From Table 4 and Table 5, the following is clear.

Examples 2-1 to 2-16 were all excellent in antistatic property, transparency and appearance of the molded product. On the other hand, in Comparative Example 2-1, 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.

[0219] 7. Manufacture and evaluation of adhesive films

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.).

On the other hand, the 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.

[0220] Thereafter, 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. Using this adhesive film, 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.

[0221] [Table 6]

Table 6

7] Table 7

8] Table 8

From Table 6 to Table 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.

In addition, the degree of warping of the adhesive films of Examples 3-12 and 3-13 (100 mm × 100 mm) after being allowed to stand for 1 hour at a temperature of 80 ° C. was observed. 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.

[0225] Example 3'— 1 to ^ 1 13 and Comparative Example 3 '— 1 to ^ 1 2

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 μm was formed on the polyethyleneimine layer side of the film by extrusion lamination. Using this adhesive film, 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.

From the results shown in Table 9, the following is clear.

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.

On the other hand, 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.

[0226] [Table 9] Table 9

[0227] 8. Production and evaluation of 3-layer sheet

Experimental example 1 2 to 1 9

In order to produce a three-layer type sheet as shown in FIG. 4, the above components (A), (B), (C) and (E) are used as the composition for forming the first layer and the third layer. After mixing with a hencil mixer at the blending ratio shown in Table 10, the mixture was melt-kneaded using a twin-screw extruder (cylinder set temperature; 220 ° C.) to obtain pellets (antistatic resin composition). On the other hand, as the composition for forming the second layer, which is an intermediate layer, pellets having polymer strength described in Table 10 were used.

After sufficiently drying each of the above pellets, using a T-die extruder of type 2 and layer 3, on both sides of the second layer having a thickness of 0.8 mm, the first and third layers having a thickness of 0.1 mm A three-layer sheet with layers was obtained. Using this three-layer sheet, the antistatic property, transparency and appearance of the molded product were evaluated. The results are shown in Table 10.

[0228] [Table 10]

[0229] From Table 10, 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.

Industrial applicability

[0230] 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.

Since 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.

Brief Description of Drawings

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.

Explanation of symbols

[0232] 1, 1, and 1 "; 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.

Claims

The scope of the claims

[1] (A) Polyolefin resin (excluding the following component (B)) 30 to 95% by mass;

(However, the total of the said component (A), a component (B), and a component (C) is 100 mass%).) The antistatic resin composition characterized by the above-mentioned.

[2] Component (A) Force Polyolefin resin (A-1) containing a cyclic olefin unit and having a glass transition temperature of 60 to 200 ° C, and a polyolefin resin (A-1) containing no cyclic olefin unit ( 2. The antistatic oil composition according to claim 1, wherein the content ratio of the two (A-1) / (A-2)) is 95Z5: LZ99 (mass ratio). object.

[3] A block copolymer in which the component (C) includes a polymer block (cl) mainly comprising a conjugated diene compound unit force and a polymer block (c2) mainly comprising an aromatic beryl compound unit force and 2. The antistatic resin composition according to claim 1, which is at least one polymer selected from the group consisting of the hydrogenated product.

[4] Furthermore, at least one antistatic agent (E) selected from the group consisting of the following component (E1), component (E2), component (E3) and component (E4) is added to the antistatic property. 2. The antistatic resin composition according to claim 1, which is contained in an amount sufficient to improve the antistatic property of the resin composition.

Ingredient (E4): nonionic surfactant.

[Chemical 1]

(Wherein R ⁵ represents a hydrocarbon group, R ⁵ ′ represents a hydrogen atom, a halogen atom or a hydrocarbon group, X represents a hydrocarbon group having a hydrogen atom, a hydrocarbon group, a urethane residue or an ester residue. Or represents a hydrophilic group, and m represents a number of 1 or more.

[Chemical 2]

[5] (A) Polyolefin resin (excluding the following component (B)) 0 to 59% by mass;

(However, the total of the above component (A), component (B) and component (C) is 100% by mass)

. ) Antistatic 'adhesive resin composition characterized by that.

[6] The above component (A) 0 to 40% by mass, the above component (B) 6 to 25% by mass, and the above component (C) 35 to 9

(However, the total of the component (A), the component (B) and the component (C) is 100% by mass.) The antistatic adhesive rubber composition according to claim 5 object.

[7] The component (A) force includes a cyclic olefin unit and has a glass transition temperature of 60 to 200 ° C. Polyolefin resin (A-1) and polyolefin resin (A-2) that does not contain a cyclic olefin unit, and the ratio of both ((A-1) / (A-2) ) Is from 95Z5 to: LZ99 (mass ratio).

[8] A block copolymer in which the component (C) comprises a polymer block (cl) mainly comprising a conjugated diene compound unit force and a polymer block (c2) mainly comprising an aromatic beryl compound unit force and 7. The antistatic adhesive resin composition according to claim 6, which is at least one polymer selected from the group consisting of the hydrogenated product.

[9] Furthermore, at least one antistatic agent (E) selected from the group consisting of the following component (E1), component (E2), component (E3) and component (E4) is added to the antistatic agent. 7. The antistatic pressure-sensitive adhesive composition according to claim 6, which is contained in an amount sufficient to improve the antistatic property of the adhesive resin composition.

Ingredient (E4): nonionic surfactant.

[Chemical 3]

[Chemical 4]

[10] The component (A) is polyolefin (Α'-1) and polyolefin (Α'-2) modified with Ζ or a functional group, and the component (C) is a conjugate conjugated compound unit. And a hydrogenated product of a polymer mainly composed of aromatic beer compound units, and the above component (Α) 0 to 59% by mass

The antistatic pressure-sensitive adhesive composition according to claim 5, comprising 3 to 60% by mass of the component (Β) and 40 to 97% by mass of the component (C).

[11] A block copolymer in which the component (C) comprises a polymer block (cl) mainly comprising a conjugated diene compound unit force and a polymer block (c2) mainly comprising an aromatic beryl compound unit force and The polymer is at least one polymer selected from the group consisting of the hydrogenated product.

10. The antistatic pressure-sensitive adhesive composition according to 10.

[12] The hydrogenation rate of the part of the component (C), which also has a conjugated unity compound unit force, is 10 to: L00

The antistatic adhesive rubber composition according to claim 11, wherein the antistatic adhesive composition is%.

[13] A support made of a thermoplastic polymer composition, disposed on at least one side of the support, and the antistatic adhesive resin according to any one of claims 5 to 12. An adhesive film comprising: an antistatic adhesive layer comprising the composition.

[14] The thermoplastic polymer composition is a polyolefin resin composition, and the antistatic adhesive layer has an antistatic adhesive composition according to any one of claims 5 to 9. The pressure-sensitive adhesive film according to claim 13.

15. The pressure-sensitive adhesive film according to claim 14, wherein the polyolefin resin-based resin composition is the antistatic resin composition according to any one of claims 1 to 4.

16. The pressure-sensitive adhesive film according to claim 13, wherein the antistatic pressure-sensitive adhesive layer comprises the antistatic pressure-sensitive adhesive composition according to any one of claims 10 to 12.

[17] The viscosity according to claim 16, wherein the thermoplastic polymer composition is a styrene-based resin composition. Chaohu Inolem.

[18] A protective film for a display device, comprising the adhesive film according to any one of claims 13 to 17.

[19] A molded article comprising the antistatic resin composition according to any one of [1] to [4].

20. The molded article according to claim 19, which is a film.

[21] Production of pressure-sensitive adhesive film comprising a step of co-extruding the thermoplastic polymer composition and the antistatic adhesive pressure-sensitive resin composition according to any one of claims 5 to 12. Method.

[22] The thermoplastic polymer composition is a polyolefin resin composition, and the antistatic adhesive composition is the composition according to any one of claims 5 to 9. Item 22. The method for producing an adhesive film according to Item 21.

[23] The strength of the polyolefin-based resin composition according to any one of claims 1 to 4, wherein the antistatic resin composition according to any one of claims 1 to 4.

[24] The method for producing an adhesive film according to [21], wherein the antistatic adhesive resin composition has the composition according to any one of claims 10 to 12.

25. The method for producing an adhesive film according to claim 24, wherein the thermoplastic polymer composition is a styrene-based resin composition.