WO2007105446A1

WO2007105446A1 - Multilayer sheet and molded article

Info

Publication number: WO2007105446A1
Application number: PCT/JP2007/053278
Authority: WO
Inventors: Masaaki Mawatari
Original assignee: Techno Polymer Co., Ltd.
Priority date: 2006-02-23
Filing date: 2007-02-22
Publication date: 2007-09-20
Also published as: JP5193474B2; CN101405138B; CN101405138A; JP2007253614A; TW200732149A

Abstract

Disclosed is a multilayer sheet which is excellent in antistatic property, chemical resistance, impact resistance, surface appearance and vacuum formability. Specifically disclosed is a multilayer sheet comprising a layer of the component (A) described below and another layer of the component (B) described below. Component (A): an antistatic resin composition containing 7-91% by mass of an olefin resin (A-1); 5-50% by mass of a (co)polymer (A-2) of a vinyl monomer containing a rubber-reinforced styrene resin and/or an aromatic vinyl compound; 2-50% by mass of a block copolymer or a hydrogenated product thereof (A-3) which contains a polymer block of an aromatic vinyl compound and a polymer block of a conjugated diene compound; and 2-60% by mass of a block copolymer (A-4) containing an olefin polymer block and a hydrophilic polymer block Component (B): an olefin resin composition containing 60-97% by mass of a polypropylene resin (B-1) having a melt flow rate of not more than 2.0 g/10 min; and 3-40% by mass of a polyethylene resin (B-2) having a melt flow rate of not more than 2.0 g/10 min

Description

Specification

Multi-layer sheets and molded products

Technical field

[0001] The present invention relates to a multilayer sheet excellent in antistatic property, chemical resistance, impact resistance, surface appearance, and vacuum formability, and a molded article comprising the multilayer sheet.

[0002] Polyolefin resin such as polypropylene is excellent in chemical resistance, heat resistance, fluidity, and the like, and is therefore widely used in the electrical / electronic field, the consumer electronics field, the vehicle field, the sanitary field, and the like. However, since this resin has a drawback that it is easily charged, it is used in a device that is damaged by static electricity, for example, a liquid crystal display device, a plasma display, a semiconductor peripheral material, a clean room, or the like. It was difficult to use for various parts, sheets, films, etc. to be handled. For the purpose of improving such drawbacks, Patent Document 1 and Patent Document 2 propose that a specific antistatic agent is blended, but the antistatic property is not long enough and the antistatic property is sufficient. There was a problem such as not. In addition, as a method for maintaining antistatic properties, Patent Document 3 proposes that a specific polymer is blended with polyolefin resin, but there is a problem that antistatic properties are not sufficiently exhibited.

[0003] On the other hand, rubber-reinforced styrene-based resins such as ABS resin are excellent in mechanical strength such as impact resistance, moldability, and rigidity, and also in the surface appearance of molded products. · Widely used in the home appliance field, vehicle field, sanitary field, etc., but depending on the intended use, there was a need for further improvement in chemical resistance, which is insufficient in chemical resistance. Further, these styrene-based resins also have the problem of static electricity damage as described above, and these improvements have been desired. Patent Document 4 proposes that a polyamide elastomer is blended with a styrene-based resin such as ABS resin, but there is a problem that antistatic properties are not sufficiently exhibited.

From the above situation, as a result of intensive studies, a material having excellent antistatic properties by blending a block copolymer having an olefin polymer block and a hydrophilic polymer block into a composition comprising polyolefin resin and ABS resin. The company applied for a patent to obtain a patent (Patent Document 5). However, the multilayer sheet using this material may have insufficient vacuum formability.

[0004] Patent Document 1: Japanese Patent Laid-Open No. 4258258 Patent Document 2: Japanese Patent Laid-Open No. 2000-313875

Patent Document 3: Japanese Patent Laid-Open No. 2001-278985

Patent Document 4: Japanese Patent Laid-Open No. 60-23435

Patent Document 5: Japanese Unexamined Patent Application Publication No. 2005-154730

Disclosure of the invention

Problems to be solved by the invention

[0005] An object of the present invention is to provide a multilayer sheet excellent in antistatic property, chemical resistance, impact resistance, surface appearance, and vacuum formability. Another object of the present invention is to provide a molded article comprising the multilayer sheet.

Means for solving the problem

[0006] As a result of intensive studies to achieve the above object, the present inventors have determined that a specific amount of a layer made of a specific antistatic resin composition, a specific polypropylene resin, and a specific polyethylene resin. The inventors have found that the object of the present invention can be achieved by laminating layers having combined compositional strength to form a multilayer sheet, and have completed the present invention.

That is, according to the present invention, there is provided a multilayer sheet comprising at least a layer having the following component (A) and a layer having the following (B) component force.

(A) component: Olefin-based rosin (A-1) 7 to 91% by mass,

Rubber-reinforced styrene resin obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound in the presence of a rubber polymer, and Z or a (co) polymer of the vinyl monomer ( A 2) 5-50% by mass,

Aromatic belief compound strength Block copolymer containing a main polymer block and a polymer block mainly composed of a conjugated Jen compound, and at least one kind selected from the group consisting of its hydrogenated power Polymer (A-3) 2-50% by mass,

A block copolymer containing an olefin polymer block and a hydrophilic polymer block (A 4) 2 to 60% by mass;

(A-1), (A-2) component, (A-3) and (A-4) components are 100% by mass in total).

Ingredient (B): Melt flow rate (JIS K7210: 1999, 230. C, measured at 2.16 kg load) . OgZlO min following polypropylene榭脂and (B- 1) 60 to 97 weight ^_0/0, melt Furore one Bok (JIS K6922- 2, 190.C, 2. measured at 16kg load) force. The following OgZlO min polyethylene emissions system榭脂(B- 2) Orefin based榭脂composition comprising 3 to 40 weight _{^0/0 using.}

The layer made of the component (B) may be foamed. In the case where a foam laminated sheet having a high antistatic property and a smooth surface and an excellent surface appearance is required, the component (A) is composed of 7-30% by mass of the olefin-based resin (A-1). , The (co) polymer (A-2) 5-20% by mass, the polymer (A-3) 15-50% by mass, the block copolymer (A-4) 20-6

Antistatic resin composition containing 0% by mass (however, the above component (A-1), component (A-2))

The total of (A-3) and (A-4) components is preferably 100% by mass).

According to another aspect of the present invention, there is provided a molded product characterized by vacuum forming the multilayer sheet.

The invention's effect

[0007] The present invention comprises a layer comprising the above specific antistatic resin composition, and a polyolefin resin comprising the polypropylene resin and the polyethylene resin having the above specific melt flow rate. Since a multilayer sheet is composed of layers, a sheet excellent in antistatic property, chemical resistance, impact resistance, surface appearance, and vacuum formability can be obtained. Thus, a molded product excellent in the above-mentioned various properties can be obtained.

BEST MODE FOR CARRYING OUT THE INVENTION

[0008] 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 Z or methacryl,

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

[0009] The olefin-based resin (A-1) related to the antistatic resin composition (A) of the present invention is an olefin-based resin having at least one kind of olefins having 2 to 10 carbon atoms. The polymer (excluding the component (A-4) described later). These olefin fins (A-1) can be used singly or in combination of two or more.

Examples of olefins used in the formation of olefin fins (A-1) include ethylene and propylene, butene-1, 1, pentene 1, hexene 1, 3-methinolevene 1, 4-methylpentene 1, 3- Α-Olefin such as methylhexene 1 and norbornene Cyclic olefin fins and the like. These can be used alone or in combination of two or more. Of these, ethylene, propylene, butene-1,1,3-methylbutene 1,4-methylpentene 1, and norbornene are preferred!

Other monomers that can be used as needed for the formation of olefin fin resin (A-1) include 4-methyl-1,4 monohexagen, 5-methyl-1,4 monohexagen, Non-conjugated gens such as 7-methyl-1,6-octadiene and 1,9-decadiene.

[0010] As the olefin-based resin (A-1), polypropylene, a polymer mainly containing a propylene unit such as propylene'ethylene copolymer, polyethylene, and ethylene'norbornene copolymer are particularly preferable, polypropylene, Propylene 'is a polymer mainly containing propylene units such as ethylene copolymer. These may be used alone or in combination. As the propylene / ethylene copolymer, it is particularly preferable to use a random type in view of the sheet surface appearance when a random copolymer, a block copolymer, or the like is used. As the polyethylene, any one of high density polyethylene, low density polyethylene, linear low density polyethylene, and the like can be used.

As the olefin fin resin of the present invention, those produced by a known polymerization method can be used, and examples thereof include a high pressure polymerization method, a low pressure polymerization method, and a metamouth catalyst polymerization method.

Furthermore, as the polyolefin resin used in the present invention, those obtained by removing the polymerization catalyst or modified with an acid anhydride, carboxyl group, epoxy group or the like can be used.

[0011] The olefin-based resin (A-1) may or may not have crystallinity, but it is preferable to use at least one having a crystallinity of 10% or more by X-ray diffraction at room temperature.

In addition, it is preferable to use at least one type of olefin-based resin (A-1) having a melting point of 40 ° C or higher measured according to JIS K7121.

When polypropylene resin is used as the component (A-1) of the present invention, the melt flow rate measured at 230 ° C. and 2.16 kg load in accordance with JIS K7210: l999 is preferably from 0.01 to 500gZlO min., More preferably 0.05-: LOOgZlO min. Is used, the melt flow rate measured in accordance with JIS K6922-2 is preferably 0.01 to 500 gZlO, more preferably 0.05 to LOOgZlO.

[0012] The amount of the component (A-1) constituting the component (A) of the present invention is used in accordance with the components (A-1), (A-2), (A-3), and ( A-4) Of the total 100% by mass of the component, 7 to 91% by mass, preferably 10 to 85% by mass, more preferably 20 to 80% by mass, and particularly preferably 20 to 75% by mass. In the case where a foamed laminated sheet having a smooth surface and an excellent surface appearance of the sheet is required, the content is preferably 7 to 30% by mass. If the amount used is less than mass%, the impact resistance, antistatic property, chemical resistance, surface appearance and vacuum formability are inferior, and if it exceeds 91 mass%, the antistatic property and impact resistance are inferior.

[0013] The component (A-2) of the present invention comprises a rubber-reinforced styrene obtained by polymerizing a vinyl monomer (b) containing an aromatic vinyl compound in the presence of a rubbery polymer (a). And (co) polymers of the system resin and Z or the vinyl monomer (b). The latter (co) polymer is obtained by polymerizing a vinyl monomer (b) containing an aromatic vinyl compound in the absence of the rubbery polymer (a).

Component (A-2) of the present invention contains at least one polymer obtained by graft polymerization of vinyl monomer (b) in the presence of rubbery polymer (a) from the viewpoint of impact resistance. Is preferred. The content of the rubbery polymer (a) is preferably 3 to 80% by mass, more preferably 5 to 70% by mass, particularly preferably 10 to 60% by mass, with the component (A-2) being 100% by mass. is there.

[0014] The rubbery polymer (a) is not particularly limited, but polybutadiene, butadiene 'styrene copolymer, butadiene' acrylonitrile copolymer, ethylene 'propylene copolymer, ethylene' propylene 'non-conjugated copolymer. Polymers, ethylene 'butene-1 copolymer, ethylene' butene-1 non-conjugated gen copolymer, acrylic rubber, silicone rubber, silicone 'acrylic IPN rubber, component (A-3) below These can be used alone or in combination of two or more.

Of these, polybutadiene, butadiene styrene copolymer, ethylene propylene copolymer, ethylene propylene non-conjugated gen copolymer, acrylic rubber, silicone rubber, and the following component (A-3) are preferable. The butadiene 'styrene copolymer used here may be either a block copolymer or a random copolymer. [0015] The gel content of the rubbery polymer (a) is not particularly limited, but when the component (a) is obtained by emulsion polymerization, the gel content is preferably 98% by mass or less. More preferably, it is 40-98 mass%. Within this range, it is possible to obtain an antistatic resin composition that gives a multilayer sheet particularly excellent in impact resistance.

In addition, the said gel content rate can be calculated | required by the method shown below. In other words, the rubber polymer lg was put into 100 ml of toluene, 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 W grams) were heated at 80 ° C for 6 hours. Dry in vacuum, weigh (assumed to be W grams), and calculate using the following formula (1).

2

[0016] Gel content (mass ⁰ / o) = [{W (g) — W (g)} Zl (g)] X 100 (1)

twenty one

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 and the like during the production of the rubbery polymer.

[0017] Examples of the aromatic belief compound constituting the above-mentioned bulle monomer (b) include styrene, exmethylstyrene, hydroxystyrene and the like. These may be used alone or in combination of two or more. The above can be used in combination. Of these, styrene and a-methylstyrene are preferred.

[0018] Other bur monomers that can be copolymerized with aromatic beryl compounds include vinylcyan compounds, (meth) acrylic acid ester compounds, maleimide compounds, and various other functional groups. Examples thereof include unsaturated compounds. Preferably, the vinyl monomer (b) comprises an aromatic bulle compound as an essential monomer component, and, if necessary, a cyanide vinyl compound or a (meth) acrylate ester compound. And at least one of various other functional group-containing unsaturated compounds, if necessary, is used as a monomer component. Used together. Other various functional group-containing unsaturated compounds include unsaturated acid compounds, epoxy group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, oxazoline group-containing unsaturated compounds, acid anhydride group-containing unsaturated compounds, substituted or unsubstituted And amino group-containing unsaturated compounds. The above various other functional group-containing unsaturated compounds can be used alone or in combination of two or more.

[0019] The cyanobi-loui compound used here includes acrylonitrile and methatalonitrile. These may be used alone or in combination of two or more. Use of cyanbi-louis compound provides chemical resistance. In the case of using a cyanobyl compound, the amount used is preferably 1 to 60% by mass, more preferably 5 to 50% by mass in the component (b).

Examples of the (meth) acrylic acid ester compound include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like. Two or more types can be used in combination.

Use of a (meth) acrylic acid ester compound is preferable because the surface hardness is improved. When the (meth) acrylate ester compound is used, the amount used is preferably 1 to 80% by mass, more preferably 5 to 80% by mass in the component (b).

Examples of maleimide compounds include maleimide, N-phenol maleimide, N-cyclohexyl maleimide and the like, and these can be used alone or in combination of two or more. In order to introduce a maleimide unit, maleic anhydride may be copolymerized and then imidized. When a maleimide compound is used, heat resistance is imparted. When a maleimide compound is used, the amount used thereof is preferably 1 to 60% by mass, more preferably 5 to 50% by mass, in component (b).

[0020] 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 of two. 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.

[0021] 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, and 2-hydroxyethyl methacrylate. , 2-hydroxyxetyl acrylate, N- (4-hydroxyphenol) maleimide, and the like. These can be used alone or in combination of two or more.

Examples of the unsaturated compound containing an oxazoline group include buroxazoline. Can be used singly or in combination of two or more.

Examples of the acid anhydride group-containing unsaturated compound include maleic anhydride, itaconic anhydride, citraconic anhydride and the like, 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-acetylbutylamine, acrylic There are amine, methacrylamine, N-methylacrylamine, acrylamide, N-methylacrylamide, p-aminostyrene, etc., and these can be used alone or in combination of two or more. .

When the above other various functional group-containing unsaturated compounds are used, when the styrene-based resin and other polymers are blended, the compatibility between them may be improved. Preferred monomers for achieving a strong effect are epoxy group-containing unsaturated compounds, unsaturated acid compounds, and hydroxyl group-containing unsaturated compounds.

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 component (A-2), and is 0. 1 to 20% by mass is preferable, and 0.1 to 10% by mass is more preferable.

The amount of the monomer other than the aromatic vinyl compound in the vinyl monomer (b) is preferably 10 to 95% by mass when the total of the vinyl monomers (b) is 100% by mass, More preferably, it is 10-90 mass%, Most preferably, it is 15-80 mass%. More preferable combinations of the monomers constituting the bur monomer (b) include styrene Z acrylonitrile, styrene Z methyl acrylate, styrene / acrylonitrile / methyl methacrylate, styrene / atari mouth-tolyl Z glycidyl methacrylate. Styrene Z acrylonitrile Z2-hydroxyethyl methacrylate, styrene Z acrylonitrile Z (meth) acrylic acid, styrene ZN-phenol maleimide, styrene Z methyl methacrylate Z cyclohexyl maleimide, etc. Styrene Z acrylonitrile and a more preferable combination of monomers polymerized in the presence of the rubbery polymer (a) are styrene Z acrylonitrile = 65Z 45 to 90Z10 (mass ratio), styrene スチレン methyl methacrylate = 80Ζ20 ~ 20 ~ 80 (mass ratio) , Styrene / acrylonitrile / methyl methacrylate, styrene content of 20 to 80 mass ^_0/0, § Krilo - Total tolyl and methyl methacrylate is of any range of 20 to 80 wt%, particularly preferably styrene Z acrylonitrile is 70Z30 to 85Z15 (mass ratio).

[0023] The component (ii-2) of the present invention can be produced by a known polymerization method, for example, emulsion polymerization, bulk polymerization, solution polymerization, suspension polymerization, or a polymerization method combining these. Among these, preferred polymerization methods for the polymer obtained by (co) polymerizing the vinyl monomer (b) in the presence of the rubbery polymer (a) are emulsion polymerization and solution polymerization. On the other hand, the polymer obtained by (co) polymerizing the vinyl monomer (b) in the absence of the rubbery polymer (a) is preferably polymerized by bulk polymerization, solution polymerization, suspension polymerization. And emulsion polymerization.

[0024] In the case of producing by emulsion polymerization, a polymerization initiator, a chain transfer agent, an emulsifier, and the like are used, and any known one 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, azobisisobutyl mouth -Trill and the like.

Further, there are various reducing agents, sugar-containing iron pyrophosphate formulations, sulfoxylate treatments and the like as polymerization initiation assistants, and it is particularly preferable to use a redox system.

Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and n-hexyl mercaptan, terpinolenes, and -methylstyrene dimer.

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.

[0025] Incidentally, in the emulsion polymerization, the rubber polymer ( _a ) and the vinyl monomer (b) are used in such a manner that the vinyl monomer is present in the presence of the rubber polymer ( _a ) in the total amount. (b) may be added at once and polymerized, or divided or continuously added for polymerization. A part of the rubber polymer (a) may be added during the polymerization. [0026] After the emulsion polymerization, the obtained latex is usually coagulated with a coagulant, washed with water and dried to obtain the (A-2) component powder of the present invention. At this time, the latex of two or more components (A-2) 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.

[0027] The solvent that can be used in the case of producing the component (A-2) by solution polymerization is an inert polymerization solvent that is used in ordinary radical polymerization, and examples thereof include aromatic carbonization such as ethylbenzene and toluene. Examples thereof include ketones such as hydrogen, methyl ethyl ketone, and acetone, acetonitrile, dimethylformamide, and N-methylpyrrolidone.

The polymerization temperature is preferably in the range of 80 to 140 ° C, more preferably 85 to 120 ° C. In the polymerization, a polymerization initiator may be used, or polymerization may be performed by thermal polymerization without using a polymerization initiator. As polymerization initiators, organic peroxides such as ketone peroxide, dialkyl peroxide, disilver oxide, peroxyester, hydride peroxide, azobisisobutyl-tolyl, benzoyl peroxide, 1, Gamma-azobis (cyclohexane-1-carbotolyl) and the like are preferably used.

Further, when a chain transfer agent is used, for example, mercabtans, terpinolenes, oc-methylstyrene dimers and the like 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 component (A-2) obtained by the above polymerization methods is preferably 10, OOOppm or less, more preferably 5, OOOppm or less.

[0028] In addition, the polymer component obtained by polymerizing the vinyl monomer (b) in the presence of the rubber polymer ( _a ) usually contains the above-mentioned bull monomer (b). The graft copolymerized with the polymer (a) and the rubbery polymer are grafted, and an ungrafted component [(co) polymer of the above vinyl monomer (b)] is contained.

The graft ratio of the component (A-2) is preferably 20 to 200% by mass, more preferably 30 to 150% by mass, and particularly preferably 40 to 120% by mass. The graft rate is expressed by the following formula (2). It can be obtained more. [0029] Graft ratio (mass%) = {(Dc-3) 3} 100 "'(2)

In the above formula (2), T is (A-2) Component lg is added to 20 ml of acetone (however, if rubbery polymer ( _a ) uses acrylic rubber, acetonitrile), shaker The mass (g) of insoluble matter obtained by shaking for 2 hours and then centrifuging for 60 minutes with a centrifuge (rotation speed: 23, OOOrpm) to separate insoluble and soluble components. S is the mass (g) of the rubbery polymer contained in the (A-2) component lg.

[0030] Further, the intrinsic viscosity (r?) Of the component (A-2) related to the present invention (however, when the rubbery polymer ( _a ) uses acrylic rubber, acetonitrile) ] (Measured at 30 ° C. using methyl ethyl ketone as a solvent) is preferably 0.2 to 1.2 dlZg, more preferably 0.2 to 1. OdlZg, particularly preferably 0.3 to 0. 8dlZg.

Average particle size of grafted rubber polymer particles dispersed in component (A-2) related to the present invention ί, <<ま 500 ~ 30, OOOA, 【Preferred <ま 1, 1, 000 ˜20, ΟΟθΑ, especially [1,500-8,000 範囲 is preferable. The average particle diameter can be measured by a known method using an electron microscope.

[0031] The amount of the component (A-2) constituting the component (A) of the present invention is as follows: (A-1) component, (A-2) component, (A-3) component, and ( A-4) The total of 100% by mass of the component is 5 to 50% by mass, preferably 7 to 50% by mass, more preferably 7 to 38% by mass, and particularly preferably 10 to 30% by mass. When a foamed laminated sheet having a smooth surface and an excellent surface appearance of the sheet is required, the content is preferably 5 to 20% by mass. If it is less than 5% by mass, the antistatic property, impact resistance and surface appearance are poor, and if it exceeds 50% by mass, the chemical resistance is poor.

[0032] The component (A-3) of the present invention is a polymer block mainly composed of an aromatic vinyl compound (A

-3- Block copolymer (A- 3-a) containing 1) and polymer block (A- 3-2) mainly composed of conjugated Jen compound and its hydrogenated product (A- 3- b) At least one polymer selected from the group of forces.

[0033] Examples of the aromatic beer compound used herein include styrene, α-methylstyrene, hydroxystyrene, and the like, preferably styrene and α-methylstyrene, and particularly preferably. Styrene. Conjugated compounds include butadiene, isoprene, hexagene, 2,3-dimethyl-1,3-butadiene, 1,3-pentagen, and the like, preferably butadiene and isoprene. These can be used alone or in combination of two or more. Further, the block (A-3-2) may be a block in which two or more kinds of conjugated genie compounds are used and are combined in any form of random, block, and taper. Further, (A-3-2) may contain a taper block in which the aromatic belief compound gradually increases in the range of 1 to 10, and the polymer block (A-3-2) ) Polymer blocks having different vinyl bond contents derived from the conjugated diene compound may be appropriately copolymerized.

[0034] The structure of the component (A-3) of the present invention is preferably a polymer represented by the following formulas (I) to (III) or a hydrogenated product thereof.

(A-B) to (1)

Y

(A-B) -X…)

Y

Α- (Β-Α) · '· (ΙΠ)

ζ

(In structural formulas (I) to (III), A is a polymer block mainly composed of an aromatic vinyl compound, and if it is a polymer block that is substantially aromatic vinyl compound, A polymer block containing 90% by mass or more, more preferably 99% by mass or more of an aromatic vinyl compound is preferable. It is a copolymer of a homopolymer or another monomer such as an aromatic vinyl compound and a conjugate conjugated compound, X is a residue of a coupling agent, Y is an integer of 1 to 5, Z Each represents an integer from 1 to 5.)

[0035] In the component (A-3) of the present invention, the use ratio of the aromatic vinyl compound and the conjugated Jen compound is such that the aromatic vinyl compound Z conjugated Jen compound = 10 to 70 Z30 to 90% by mass. preferred instrument further preferably 15~65Ζ35~85 mass%, particularly preferably from 20 to 60 Zeta40～80 mass ^_0/0.

[0036] A block copolymer composed of an aromatic beryl compound and a conjugated gen y compound is known in the technical field of key-on polymerization, such as Japanese Patent Publication No. 47-28915. Disclosure in Japanese Patent Publication No. 47-3252, Japanese Patent Publication No. 48-2423, and Japanese Patent Publication No. 48-20038 Has been. Further, a method for producing a polymer block having a tapered block is disclosed in JP-A-60-81217 and the like.

[0037] The content of vinyl bonds (1, 2- and 3, 4 bonds) derived from the conjugated conjugated compound of the component (A-3) of the present invention is preferably in the range of 5 to 80%, Number average molecular weight of component (A-3) of the present invention [Preferably, <10,000 or 1,000 to 1,000,000, more preferably <ί, 20,000 or more, 500,000, particularly preferably 20 , 000-200,000. Of these, the number average molecular weight of the heel part represented by (Ι) to (ΠΙ) above is in the range of 3,000 to 150,000, and the number average molecular weight of B part is in the range of 5,000 to 200,000. I like it!

[0038] Adjustment of the amount of bull bonds of conjugation compounds is possible by adjusting N, N, Ν ', N'-tetramethylethylenamine, trimethinoreamine, triethenoreamine, diazocyclo (2, 2, 2) octamine, etc. These amines, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether and other ethers, thioethers, phosphines, phosphoamides, alkylbenzene sulfonates, potassium and sodium alkoxides, and the like can be used.

A polymer in which a polymer molecular chain is extended or branched through a coupling agent residue using a coupling agent after the polymer is obtained by the above method is also preferable as the component (Α-3) of the present invention. Although included, coupling agents used here include jetyl adipate, divinyl benzene, methyl dichlorosilane, silicon tetrachloride, butyl trichloro silicon, tetra black tin, butyl tri black tin, dimethyl black silicon, tetra black neck Examples include germanium, 1,2-dibromoethane, 1,4 chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized amateur oil, tolylene diisocyanate, 1,2,4 benzene triisocyanate, and the like.

[0039] Among the above block copolymers, those having favorable impact resistance also have a taper block in which aromatic vinyl compounds are gradually increased in the range of 1 to 10 in the block (Α-3-2). Polymer and cage or coupled radial block type.

[0040] In addition, as the (Α-3) component, the block copolymer itself may be used, or a partially or completely hydrogenated carbon-carbon double bond in the conjugate moiety may be used. it can. From the low-temperature impact properties of the obtained composition, it is preferable to use a non-hydrogenated one or a hydrogenation rate of less than 90%. From the viewpoint of (photo) properties, it is preferable to use a product hydrogenated by 90% or more.

[0041] The hydrogenation reaction of a block copolymer containing a polymer block mainly composed of an aromatic vinyl compound obtained by the above method and a polymer block mainly composed of a conjugated diene compound is carried out by a known method. In addition, the target polymer can be obtained by adjusting the hydrogenation rate by a known method. Specific methods include JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-63-5401, JP-A-2-133406, There is a method disclosed in Kaihei 1-297413.

[0042] The block copolymer (A-3-a) and its hydrogenated product (A-3-b) are composed of a block polymer, a Z polymer, or a graft polymer (provided that the component (A — Except 2)) may be chemically bonded.

100% by mass of the block copolymer (A-3-a) and other polymer chemically bonded to the hydrogenated product (A-3-b) are chemically bonded. The object of the present invention can be achieved as long as at least 10% by mass of other polymers are chemically bonded.

[0043] The block copolymer (A-3-a) and the hydrogenated product (A-3-b) thereof and other polymers bonded as a block polymerization are preferably aromatic polycarbonate and Z or polyurethane. More preferably, it is an aromatic polycarbonate. The aromatic polycarbonate-bonate block copolymer mixture can be produced, for example, by the method described in JP-A-2001-220506. Furthermore, it can be obtained as TM-S4 L77, TM-H4L77 (trade name) of TM polymer series made by KURARENE.

[0044] In addition, a particularly preferable method for graft polymerizing the other polymer to the block copolymer (A-3-a) and the hydrogenated product (A-3b) is the block copolymer ( In this method, a vinyl monomer is graft-polymerized in the presence of A-3a) and its hydrogenated product (A-3-b). As the vinyl monomer, (A-2) component vinyl monomer (b) (however, it may or may not be the same as that used in component (A-2)). Preferably used. As the method for graft polymerization, emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization and the like described above for the component (A-2) can be used, and solution polymerization and bulk polymerization are more preferable. [0045] The component (A-3) of the present invention is 100% by mass in total of the components (A-1), (A-2), (A-3), and (A-4) of the present invention. 2 to 50% by mass, preferably 5 to 45% by mass, more preferably 7 to 40% by mass, particularly preferably 10 to 35% by mass, having high antistatic properties and a smooth surface. When a foamed laminated sheet having an excellent sheet surface appearance is required, it is preferably 15 to 50% by mass. If it is less than 2% by mass, the impact resistance is inferior, and if it exceeds 50% by mass, the impact resistance and the sheet surface appearance are inferior.

[0046] The component (A-4) of the present invention is a block copolymer containing an olefin polymer block (A-4-1) and a hydrophilic polymer block (A-4-2). It may be a diblock or a multiblock that is more than a triblock. The olefin polymer block (A-4-1) is a (co) polymer of olefins. Examples of olefins used here are ethylene and α-olefins such as propylene, butene-1, hexene 1, 3-methylbutene 1, 4-methylpentene 1, 3-methylhexene 1, etc. Further, there are cyclic olefins such as norbornene, and preferably ethylene, propylene, butene-1, 1,3-methylbutene 1, 4-methylpentene 1, and norbornene. In addition, non-conjugated gens such as 4-methyl-1,4 monohexagen, 5-methyl-1,4 monohexagen, 7-methyl-1,6-octadiene, 1,9-decadiene, etc. are used as part of the polymer component. Can be used. The number average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) of the olefin polymer block (Α—4-1) is preferably 800 to 20,000, more preferably <ί or 1, It is 00-10,000, specially preferred <ί or 1, 2000-6, 000.

[0047] The block (Α-4-1) is chemically bonded to the block (Α-4-2), and the bond includes an ester bond, an amide bond, an ether bond, a urethane bond, an imide bond, and the like. It is at least one type of bond selected by force, and has a structure in which these bonds are alternately and alternately connected through these bonds. However, unbound blocks may be included as long as they do not affect the antistatic property described later.

For this reason, the molecular ends of the block (Α-4-1) must be modified with functional groups having reactivity with the molecular functional groups at both ends of the block (Α-4-2). . These functional groups include carboxylic acid groups, hydroxyl groups, amino groups, acid anhydride groups, oxazoline groups, epoxy groups and the like. A preferred method for imparting these functional groups is a carbon-carbon unsaturated compound having the above-mentioned functional group in the component (A-41) having a carbon-carbon double bond at the molecular end obtained by the thermal degradation method. It is a method of adding.

[0048] Examples of the hydrophilic polymer of the block (A-4-2) component include polyethers, polyether-containing hydrophilic polymers, and char-on polymers.

Examples of the polyether include polyether diol, polyether diamine, and modified products thereof.

Examples of the polyether-containing hydrophilic polymer include polyether ester amide having a polyether diol segment, polyether amide imide having a polyether diol segment, polyether ester having a polyether diol segment, and polyether diamine. And polyether urethane having a segment of polyether diol or polyether diamine.

As a terion-containing polymer, a dicarboxylic acid having a sulfonyl group and the above-mentioned polyether are essential component units, and preferably 2 to 80, more preferably 3 to 60 sulfo- per molecule. Included are eron polymers having a thiol group. These may be linear or branched. Particularly preferred component (A-4 2) is polyether.

[0049] Among the polyethers, the polyether diol is represented by the general formula (IV):

H— (OA ¹ ) — OE ¹ — O CA'O), H

And general formula (V): H— (OA ² ) -0-E ² -0- (A ² 0)

m m

I can get lost. In general formula (IV), E ¹ is a residue obtained by removing a hydroxyl group from a divalent hydroxyl group-containing compound, A ¹ is an alkylene group having 2 to 4 carbon atoms, n and are the above-mentioned divalent hydroxyl group-containing compounds. Represents the number of alkylene oxides added per hydroxyl group. n (OA ¹ ) and (8 ¹ ) may be the same or different. In addition, when these are composed of two or more oxyalkylene groups, the bond form is a block. Alternatively, it may be random or a combination thereof. n and η are generally integers of 1 to 300, preferably 2 to 250, particularly preferably 10 to 100. Also, η and ηΊ may be the same or different. [0050] 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 thereof include dihydric alcohols (for example, aliphatic, alicyclic or aromatic dihydric alcohols having 2 to 12 carbon atoms), dihydric phenols having 6 to 18 carbon atoms, and diols containing tertiary amino groups.

Examples of the aliphatic dihydric alcohol include alkylene glycols such as ethylene glycol and propylene glycol, 1,4 butanediol, 1,6 hexanediol, 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 dimethanol. Examples of the aromatic dihydric alcohol include xylenediol.

Divalent phenols include monocyclic divalent phenols such as hydroquinone, catechol, resorcin, and urushiol, bisphenol A, bisphenol F, bisphenol S, 4, 4'-dihydroxydiphenol 2, 2-butane, Examples thereof include bisphenols such as dihydroxybiphenyl and dihydroxydiphenyl ether, and condensed polycyclic divalent phenols such as dihydroxynaphthalene and binaphthol.

[0051] In the general formula (V), E ² is a divalent hydroxyl group-containing compound force described in the general formula (IV) and a residue excluding the hydroxyl group, and A ² is at least partially in the general formula ( VI): —CHR—CHIT [wherein, one of R and is a group represented by the general formula (VII): —CH 0 (A ³ 0) R ″, and the other is H.

2 X In the general formula (VII), X is an integer of 1 to 10, R "is H or an alkyl group, aryl group, alkylaryl group, arylalkyl group or acyl having 1 to 10 carbon atoms. A ³ is an alkylene group having 2 to 4 carbon atoms.] And the remainder may be an alkylene group having 2 to 4 carbon atoms m (OA ² ) And π (Α ² 0) may be the same or different, and m and π are preferably integers of 1 to 300, more preferably 2 to 250, especially 10 to: L00 M and πΓ may be the same or different.

[0052] The polyether diol represented by the general formula (IV) can be produced by addition reaction of an alkylene oxide to a divalent hydroxyl group-containing compound. Alkyleneoxy Examples of the side include alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,4-butylene oxide, 2,3-butylene oxide, and 1,3-butylene oxide. Two or more of these combined systems are used. When two or more alkylene oxides are used in combination, the bond type can be random or Z or block. V, preferred as alkylene oxide, is block and Z or random addition by ethylene oxide alone and in combination with ethylene oxide and other alkylene oxides. The addition number of alkylene oxide is preferably an integer of 1 to 300, more preferably 2 to 250, and particularly preferably 10 to LOO per hydroxyl group of the divalent hydroxyl group-containing compound.

[0053] A preferred method for producing the polyether diol represented by the general formula (V) is as follows.

(A), the method of (i) etc. are mentioned.

(A) Starting from the above divalent hydroxyl group-containing compound, the general formula (VIII):

[0055] [Chemical 1]

CH ₂ -C HC H ₂ -0-(A ⁴ 0). One R ¹ (珊)

[A ⁴ in the general formula (VIII) is an alkylene group having 2 to ⁴ carbon atoms, p is an integer of 1 to 10, R ¹ is H or an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkyl aryl group. A group, an aryl group or an 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.

[0056] (ii) A method in which the above divalent hydroxyl group-containing compound is used as a starting material, and via a polyether having a chloromethyl group in the side chain. More specifically, after addition copolymerization of epichlorohydrin or epichlorohydrin and alkylene oxide to obtain a polyether having a chloromethyl group in the side chain, the polyether and C 2-4 carbon atoms are obtained. A polyalkylene glycol and R′X (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. In the presence of an alkali. [0057] As the alkylene oxide having 2 to 4 carbon atoms used here, all of those described above can be used.

In addition, a preferred component (A-4) of the present invention can be obtained by polymerizing the olefin polymer block (A-4-1) and the hydrophilic polymer block (A-42) by a known method. it can. For example, the block (A-4-1) and the block (A-4-2) can be produced by performing a polymerization reaction at 200 to 250 ° C. under reduced pressure. In the polymerization reaction, a known polymerization catalyst can be used.

[0058] 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, etc. 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.

[0059] For the purpose of further improving the antistatic property which is the object of the present invention, the component (A-4) can contain an alkali metal salt and a salt of Z or alkaline earth metal (C). . These components can be contained before polymerization of component (A-4), during polymerization of component (A-4), or after polymerization of component (A-4). Further, the component (C) may be blended when the antistatic resin composition of the present invention is produced, or may be contained by a method combined with the above method.

Examples of the component (C) include organic acids, sulfonic acids, inorganic acid salts, and halides of alkali metals such as lithium, sodium, and potassium, and alkaline earth metals such as Z, magnesium, and calcium.

[0060] Specific preferred examples of component (C) include lithium chloride, sodium chloride salt, potassium salt potassium salt, alkali metal halides such as lithium bromide, sodium bromide, potassium bromide; persalt 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; phenyl sulfonic acid, naphthyl sulfonic acid Alkali metal salts of aromatic sulfonic acids such as octyl phenyl sulfonic acid, dodecyl phenyl sulfonic acid, dibutyl phenol sulfonic acid, dinoyl phenyl sulfonic acid, etc. Alkyl benzene sulfonic acid alkali metal salts having 6 to 18 carbon atoms in the alkyl group ; Alkali metal salts such as alkylnaphthalenesulfonic acid having 2 to 18 carbon atoms in the alkyl group such as dimethylnaphthylsulfonic acid, diisopropylnaphthylsulfonic acid, dibutylnaphthylsulfonic acid, etc .; Fluorination such as trifluoromethanesulfonic acid, etc. Examples thereof include alkali metal salts such as sulfonic acid, and these can be used alone or in combination of two or more. The component (C) can be used in the range of preferably 0.001 to L0 mass%, more preferably 0.01 to 5 mass% with respect to the component (A-4) of the present invention.

[0061] of the present invention (A- 4) in the component (A- 4-1) component Z (A- 4- 2) components of preferred U, the specific rate in the range of 10~90Z10~90 mass ^_0/0 There, more preferably 20~80Ζ20~80 mass ^_0/0, and particularly preferably in the range of 30~70Ζ30~70 mass ^_0/0.

Such a block copolymer (Α-4) can be produced, for example, by the method described in JP-A-2001-278985 and JP-A-2003-48990. Component (4) can be obtained as Sanyo Kaisei Kogyo's Perezatsu 300 Series 300, 303, 200 Series 230, 201, etc.

[0062] The component (Α-4) of the present invention comprises (A-1) component, (Α-2) component, (Α-3) component, and (Α-4) component in a total of 100% by mass, 2 to 60% by mass. If it is less than 2% by mass, the antistatic property is inferior, and if it exceeds 60% by mass, the impact resistance and the sheet surface appearance are inferior. In applications where excellent chemical resistance and molded product surface appearance are required, the component (Α-4) of the present invention comprises the components (A-1), (Α-2), (Α-3), And (ii-4) in a total of 100% by mass of the component, preferably 2 to 40% by mass, more preferably 3 to 35% by mass, still more preferably 5 to 35% by mass, particularly preferably 5 to 30% by mass. It is. In applications where excellent antistatic properties are required, the component (Α—4) of the present invention includes the components (Α—1), (Α—2), (Α—3), and (Α—4). ) In a total of 100% by mass of the components, 12 to 60% by mass, preferably 20 to 60% by mass, more preferably 30 to 60% by mass, and particularly preferably 35 to 60% by mass.

[0063] The melt flow rate measured at 230 ° C and a load of 2.16 kg in accordance with JIS K7210: 1999 of the antistatic resin composition which is component (ii) of the present invention is 0.5 to 25 gZlO min. Is in the range More preferably, the content is 0.5 to 20 gZlO, and particularly preferably 1.0 to 15 g / 10 minutes, and in this range, the antistatic property, the sheet surface appearance, and the impact resistance are excellent. The melt flow rate of the component (A) can be set arbitrarily by changing the molecular weight, blending amount, etc. of the component (A-1), component (A-2), component (8-3), or component (8-4). You can change it.

[0064] The olefin-based rosin composition of component (B) of the present invention has a melt flow rate (JIS K7210:

1999, 230 ° C, measured at 2.16 kg load) 2. Polypropylene resin (B-1) with less than OgZlO content and Menoleto flow rate (JIS K6922-2, 190.C, at 2.16kg load) ¾J constant) Force S 2.0 It consists of polyethylene resin (B-2) with less than gZlO content.

Polypropylene resin (B-1) used here includes propylene homopolymers and copolymers of propylene and other monomers. Other monomers used here include Ethylene, butene-1, pentene 1, hexene 1, 3-methylbutene 1, 4-methylpentene 1, 3-methylhexene 1, and the like are particularly preferable.

Examples of propylene / ethylene copolymers include random copolymers and block copolymers, and any of them can be used. The amount of monomers other than propylene constituting the polypropylene-based resin (B-1) is preferably 0 to 60% by mass of the entire polypropylene-based resin (B-1).

As the polypropylene resin of component (B-1) used in the present invention, homopolypropylene is particularly preferable.

[0065] In accordance with JIS K7210: 1999 of component (B-1), the melt throat measured at 230 ° C and a load of 16 kg is 2. OgZlO or less, preferably 0.05 ~: L 5gZlO Minute, more preferably 0.1 to 1.4 gZlO, and particularly preferably 0.3 to 1. OgZlO. 2. If the OgZlO content is exceeded, the vacuum formability of the multilayer sheet of the present invention is poor.

[0066] The polyethylene-based resin (B-2) used in the present invention includes an ethylene homopolymer, and a copolymer of ethylene and another monomer. As monomer

, Butene 1, pentene 1, hexene 1, 3-methylbutene 1, 4-methylpentene 1, 3-methylhexene 1, norbornene, and the like.

As the polyethylene-based resin used in the present invention, an ethylene homopolymer is particularly preferable. As polyethylene, high density polyethylene, low density polyethylene, linear low density Although any polyethylene can be used, low density polyethylene is particularly preferable for the vacuum formability.

[0067] According to JIS K6922-2 of component (B-2), the melt flow rate measured at 190 ° C and 2.16 kg load is 2. OgZlO or less, preferably 0.05 ~: L 5gZlO min. More preferably, the content is 0.1 to 1.2 gZlO, and particularly preferably 0.3 to 1. OgZlO. 2. If the content exceeds OgZlO, the vacuum formability of the multilayer sheet of the present invention is poor.

[0068] The olefin-based resin composition (B) of the present invention comprises a component (B-1) and a component (B-2), and the amount used is (B-1) component Z (B-2). ) component = 60～97Z3～40 the mass%, preferably ί or 70 to 95/5 to 30 mass ^_0/0, further [this preferably ί or 70-90 / 10-30 mass ^_0/0, JP [this good It is preferably 75 to 90% to 10 to 25% by mass, and in the region where (B-1) component is less than 60% by mass and (VB-2) component force exceeds S40% by mass, the sheet appearance and vacuum formability are poor. Also, if the (Β-1) component exceeds 97% by mass and the (Β-2) component is less than 3% by mass, the vacuum formability is poor.

[0069] For the purpose of improving the antistatic property of the component (i) of the present invention, a specific compound can be blended during the production of the component (i). The specific compound used here includes a lithium salt. A non-ionic antistatic agent is preferable.

As the lithium salt compound, lithium perchlorate, lithium trifluoromethanesulfonate, bis (trifluoromethanesulfol) imide lithium, tris (trifluoromethanesulfol) methanelithium, etc. are preferably used. More preferably, it is lithium trifluoromethanesulfonate. These can be used alone or in combination of two or more. These can be obtained as Sanconol 0862-13T, AQ-50T, AQ-75T, and TBX-25 (trade names) manufactured by Sanko Chemical Co., Ltd. as solutions and masterbatches. This lithium salt compound can also be used as the component (C).

[0070] The lithium salt compound is preferably used in the range of 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts per 100 parts by mass of the component (A) of the present invention. It is used in parts by weight, particularly preferably in the range of 0.3 to 2 parts by weight. If the amount used is less than 0.01 parts by mass, the antistatic effect cannot be obtained, and if it exceeds 5 parts by mass, the impact resistance tends to decrease.

[0071] Nonionic antistatic agents include polyhydric alcohol ester compounds, amines, amides, and the like. Polyhydric alcohol ester compounds include glycerin monostearate, Glycerol monomyristate, glycerol monopalmitate, glycerol monostearate, glycerin monobehenate, glycerol monooleate, diglycerol monolaurate, diglycerol monomyristate, diglycerol monopalmitate, diglycerol monostearate, diglycerol Monobehenate, diglycerin monooleate, sorbitan monolaurate, sonorebitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monobehenate, sorbitan monolaurate, etc. One species can be used alone, or two or more species can be used in combination. Particularly preferred are those containing glycerol monostearate rate, diglycerol monostearate, glycerol monolaurate, diglycerin monolaurate, sorbitan monostearate and these at least 20 mass ^_0/0 or more

[0072] Examples of amines and amides include lauryl diethanolamine, myristyl diethanolamine, palmityl diethanolamine, stearyl diethanolamine, oleyljetanolamine, lauryl diisopropanolamine, myristyl diisopropanolamine, palmityl. Amine compounds such as diisopropanolamine, stearyl diisopropanolamine, oleyldiisopropanolamine, N, N-bishydroxyethylalkyl (alkyl group having 12 to 22 carbon atoms) amine, and lauryldiethanolamide, myristylger Tanol amide, palmityl diethanolamide, behercetanol amide, oleyl diethanolamide, lauryl diisopropanolamide, myristyl diisopropanol amide, Palmityl di-isopropanol amides, stearyl diisopropanolamine amide, there is an amide compound such as Orei distearate isopropanol amides. These can be used alone or in combination of two or more. Preferred are the above amine compounds, and more preferred are those containing at least 20% by mass of lauryl diethanolamine and stearyl diethanolamine, respectively.

[0073] For the purpose of improving the antistatic performance of the above-mentioned compounds, known additives can be blended. Illustrative of these are higher alcohols having 12 to 18 carbon atoms, lubricants, silica, calcium silicate, and the like. It is also possible to use master batches for the purpose of improving miscibility.

The nonionic antistatic agent is, for example, Kao Electro Stripper EA, TS- Available from the market as 3B, TS-6B, TS-5, TS-2B (trade name).

[0074] The nonionic antistatic agent is preferably in the range of 0.01 to: LO parts by weight, more preferably 0.1 to 8 parts by weight with respect to 100 parts by weight of the component (A) of the present invention. Particularly preferably, it is used in the range of 0.1 to 5 mass parts. If the amount used is less than 0.01 parts by mass, the effect of improving the antistatic property cannot be obtained, and if it exceeds 10 parts by mass, the sheet surface appearance tends to be inferior.

[0075] The antistatic resin composition (A) of the present invention and the olefin-based resin composition (B) of the present invention include known weathering (light) agents, antioxidants, heat stabilizers, lubricants, Silicone oil, plasticizer, sliding agent, colorant, dye, foaming agent, processing aid (ultra high molecular weight acrylic polymer, ultra high molecular weight styrene polymer), flame retardant, crystal nucleating agent, etc. can do.

[0076] In addition, a known inorganic or organic filler can be blended with the component (A) and the component (B) of the present invention. The filler used here is glass fiber, glass flake, glass fiber milled fiber, glass powder, glass bead, hollow glass bead, carbon fiber, carbon fiber milled fiber, silver, copper, brass, iron, etc. Powder or fibrous material, carbon black, tin-coated titanium oxide, tin-coated silica, nickel-coated carbon fiber, talc, calcium carbonate, calcium carbonate whisker, wollastonite, my strength, kaolin, montmorillonite There are chitolite, zinc oxide whisker, potassium titanate whisker, aluminum borate whisker, plate-like alumina, plate-like silica, organically treated smectite, aramid fiber, phenol resin, polyester fiber, etc. Can be used alone or in combination of two or more. wear.

Furthermore, for the purpose of improving the dispersibility of the filler, those treated with a known coupling agent, surface treating agent, sizing agent, etc. can be used. As the known coupling agent, silane coupling is used. Agents, titanate coupling agents, aluminum coupling agents.

The inorganic or organic filler is usually used in the range of 1 to 200 parts by mass with respect to 100 parts by mass of each of the components (A) and (B) of the present invention.

[0077] Further, the component (A) or the component (B) of the present invention includes other known polymers such as polyamide resin, polyamide elastomer, polybutylene terephthalate, polyethylene terephthalate, polyarylate, and liquid crystal polyester. Thermoplastic polyester resin, polyester error Stomer, PMMA, Methyl methacrylate 'maleimide compound copolymer, Polyphenylene ether, Polyphenylene sulfide, Aromatic polycarbonate, Thermoplastic polyurethane, Ethylene' (meth) methyl acrylate copolymer, Ethylene '(meth) An acrylic acid copolymer, epoxy resin, phenol resin, urea resin, phenoxy resin, and the like can be appropriately blended in the multilayer sheet of the present invention. B) It is provided with at least a layer having component power. When forming both layers into a sheet, the component (A) and the component (B) may be pre-melted and kneaded with each component, or each component may be used during sheeting. In this case, the components may be melted and kneaded in advance, and each component may be melted and kneaded in advance, and used together with the material.

In the case of melt-kneading in advance, each component can be carried out using various extruders, Banbury mixers, feeders, continuous-rollers, rolls and the like. When kneading, each component may be added in a lump or kneaded or added separately.

The structure of each layer of the multilayer sheet of the present invention is not particularly limited, and may be, for example, foamed or hollow. In the case of foaming the layer comprising the component (B), the foaming agent is not particularly limited. For example, a known foaming agent used for foamed polypropylene-based resin or foamed polyethylene-based resin can be used. it can. Specific examples of blowing agents include inorganic blowing agents such as carbon dioxide, air and nitrogen, volatile blowing agents such as aliphatic hydrocarbons and halogeno hydrocarbons, azodicarbonamide (ADCA), and dinitrosopentamethylenetetra. Examples include decomposable foaming agents such as amines, azobisisobutyric-tolyl, hydrazodicarbonamide, and sodium hydrogen carbonate. These can be used alone or in admixture of two or more. Of these, it is preferable to use a decomposable foaming agent that allows easy adjustment of the molding processing temperature and the amount of foaming. Moreover, there is no restriction | limiting in particular in the usage-amount of a foaming agent. In the case of a force decomposition type foaming agent, it is preferable that it is 0.1-10 mass parts with respect to 100 mass parts of foaming resin composition. When foaming the layer comprising the component (B), the olefin-based resin (A-1) is 7 to 30% by mass, and the (co) polymer (A-2) 5 to 20 is used as the component (A). The antistatic resin composition comprising 1% by mass, 15% to 50% by mass of the polymer (A-3), and 0 to 60% by mass of the block copolymer (A-4) 20 A-1) component, (A-2) The total amount of the components (A-3) and (A-4) is 100% by mass).

[0079] The multilayer sheet of the present invention comprises at least one layer that also has antistatic resin composition strength of component (A),

B) Specifically, it is sufficient to provide at least one layer composed of the olefin-based resin.

A two-layer sheet comprising a layer having component force (A) and a layer having component force (B), the layer comprising component (B) as the core layer, and the layer having component force (A) on both the front and back surfaces of the core layer The multilayer sheet of the present invention includes a three-layer sheet laminated on the sheet and a sheet multilayered more than that. Preferred are the two-layer sheet and the three-layer sheet.

The thickness of the multilayer sheet is preferably 0.2 to: LOOmm, more preferably 0.5 to 50 mm, and particularly preferably 0.5 to 5 mm.

In the multilayer sheet, the thickness of the antistatic resin composition of the present invention is preferably 10 μm or more, more preferably 30 μm or more, for the purpose of stably developing antistatic properties. Particularly preferably, it is 50 μm or more.

[0080] As the method for producing the multilayer sheet, all known methods can be used.

The following methods (1) to (3) are mentioned.

(1) A method in which the sheet of component (A) and the sheet of component (B) are produced and bonded (dry lamination method).

(2) A method of extruding and laminating the sheet or film of the component (A) at the time of extruding the component (B) using the component (A) that has been formed into a sheet or film in advance.

(3) A method of coextrusion of component (A) and component (B) (coextrusion method).

Among these, a particularly preferable method is a coextrusion method.

[0081] In the above, as a method for forming a sheet or film in advance, T-die extrusion molding, inflation molding, calendar molding, and the like are preferable. Further, when obtained by the co-extrusion method, multi-layer T-die extrusion molding and multi-layer inflation molding are preferred. Multi-layer T-die extrusion molding is particularly preferred, and extrusion is preferably performed in the range of 160 ° C to 260 ° C. .

[0082] The multilayer sheet of the present invention is excellent in antistatic property, chemical resistance, impact resistance, and surface appearance, and therefore can be used as a sheet molded product. In addition to the above properties, vacuum formability Therefore, it can be used for various purposes by forming molded products such as trays by vacuum forming. The molded product thus obtained includes cases such as relay cases, wafer cases, reticle cases, mask cases, liquid crystal trays, chip trays, hard disk (HDD) trays, CCD trays, IC trays, organic EL trays, In clean rooms such as optical pickup-related trays, LED trays, memory trays and other trays, IC carriers and other carriers, polarizing films, light guide plates, protective films such as various lenses, underlay sheets when polarizing films are cut, and partition plates Sheets or films used in vending machines, internal parts of vending machines, liquid crystal panels, hard disks, antistatic bags used for plasma panels, plastic cardboard, liquid crystal panels, soft cases for transporting plasma panels, etc. It can be used in the field of parts transportation related members.

Example

[0083] The following examples are provided to illustrate the present invention in more detail. The present invention is not limited to these examples unless they exceed the gist of the present invention. In the examples, parts and% are based on mass unless otherwise specified. Further, various measurements in Examples and Comparative Examples were based on the following methods.

[0084] [1] Evaluation method

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

(2) Average particle diameter of rubbery polymer latex;

The average particle size of the rubbery polymer latex used for forming the component (A-2) was measured by a light scattering method. The measuring machine used was LPA-3100 manufactured by Otsuka Electronics Co., Ltd., and the Mumulant method was used with 70 integrations. In addition, it was confirmed with an electron microscope that the particle diameter of the dispersed graft rubber-like polymer particles in the component (A-2) was almost the same as the latex particle diameter.

(3) Graft ratio of component (A-2); The above-described method was followed.

(4) Intrinsic viscosity [7?] Of the acetone-soluble component of component (A-2);

(5) Component (A-3) component (polymer styrene content, vinyl bond content, number average molecular weight, and hydrogenation rate);

(5-1) Bonded styrene content;

It was measured on the polymer before hydrogenation. Calibration curve force due based, was infrared method to the absorption of the phenyl groups of the 699cm ^_1 it was also determined. (5-2) Number average molecular weight;

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

(5-3) Vinyl bond amount

It was measured on the polymer before hydrogenation. Obtained by infrared method (Morello method).

(5-4) Hydrogenation rate;

Measurements were taken on the polymer after hydrogenation. It was calculated from the spectrum reduction of the unsaturated double bond of 100 MHz ¹ H-NMR ^ vector measured at 15% concentration using tetrasalt-ethylene as a solvent.

(6) Antistatic property;

Using a multi-layer sheet, according to FTMS-101 (US federal test standard), using ST ATIC DECAY METER 406D manufactured by ETS USA, applying +5000 V under 23 ° C, humidity 12% RH condition, then grounding, The time (seconds) until decay to 50 V was measured.

(7) Chemical resistance;

Using a multilayer sheet, 1% strain was applied to the test piece, isopropyl alcohol was applied, and the surface state of the sheet after being left at 23 ° C. for 72 hours was visually evaluated based on the following evaluation criteria.

○: No change

X: Large crack or break

(8) Sheet surface appearance;

The surface of the multilayer sheet was visually evaluated according to the following criteria.

◎; Smooth surface and very good

○: Appearance is smooth and smooth

X: The surface is not smooth and the appearance is poor

(9) Impact resistance

Using a multilayer sheet, the Detbon impact strength (kgf 'cm) was measured according to ASTM-D2794.

(10) Melt flow rate of antistatic resin composition (A) Using sufficiently dried pellets of component (A), the melt flow rate (gZlO content) was measured at 230 ° C and 2.16 kg load according to JIS K7210: 1999.

(11) Vacuum formability;

Vacuum forming (preheater temperature 400 ° C) was performed using the multilayer sheet, and a tray (dimensions: 400 mm × 500 mm × 50 mm) was formed.

O: The target tray molded product was obtained.

X: The sheet hangs due to preheating and cannot be molded, or the appearance of the molded product is inferior.

[0086] [2] Component of antistatic resin composition (A)

(1) (A-1) component; polypropylene resin

The following polypropylene resin manufactured by Nippon Polypro Co., Ltd. was used as the component (A-1) of the present invention. According to JIS Κ7210: 1999, it was determined ¾J at 230 ° C and 2.16kg load.

Al— 1; Novatec PP FY6C (trade name)

Homotype, melt flow rate 2.4gZlO min

A1— 2; Novatec PP MA3AH (trade name)

Homotype, melt flow rate lOgZlO min

A1— 3; Novatec PP EG6D (trade name)

Random type, melt flow rate 1. 9gZlO min

A1— 4; Novatec PP MG3ATB (trade name)

Random type, melt flow rate lOgZlO min

[0087] (2) (A-2) Component

(2-1) Production Example 1; ABS resin

Ion exchange water 75 parts, potassium rosinate 0.5 parts, tert-dodecyl mercaptan 0.1 parts, polybutadiene latex (average particle size; 3500) A, gel content: 85%) 40 parts (solid content), 15 parts of styrene, and 5 parts of Atari mouth-tolyl were heated and heated with stirring. When the internal temperature reached 45 ° C, a solution of 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate, and 0.2 parts of glucose in 20 parts of ion-exchanged water was added. added. Then, 0.07 parts of tamennoid mouth peroxide In addition, polymerization was initiated. After polymerization for 1 hour, 50 parts of ion-exchanged water, 0.7 parts of potassium rosinate, 30 parts of styrene, 10 parts of acrylonitrile, 0.05 part of tert-dodecyl mercaptan and 0.01 part of cumene hydride peroxide were added. The polymerization was continuously added over 3 hours, and the polymerization was further continued for 1 hour. Then, 0.2 part of 2,2′-methylene bis (4-ethyl-6-tert-butylphenol) was added to complete the polymerization. The latex of the reaction product was coagulated with a sulfuric acid solution, washed with water, and dried to obtain rubber-reinforced styrene-based resin A2-1. The graft ratio of this resin A2-1 was 68%, and the intrinsic viscosity [r?] Of the acetone-soluble component was 0.45 dlZg.

[0088] (2-2) Production Example 2; AS resin

Two jacketed polymerization reactors equipped with ribbon wings with an internal volume of 30 L were connected and replaced with nitrogen, and then 75 parts of styrene, 25 parts of acrylonitrile and 20 parts of toluene were continuously added to the first reactor. . A solution of tert-dodecyl mercabtan 0.12 parts and toluene 5 parts as molecular weight regulator, and 1, 1'-azobis (cyclohexane 1-carbo-tolyl) 0.1 part and toluene 5 parts as polymerization initiator Solution was continuously fed. The polymerization temperature of the first group was controlled at 110 ° C., the average residence time was 2.0 hours, and the polymerization conversion rate was 57%. The obtained polymer solution was continuously taken out from the first reaction vessel by the same amount as the styrene, acrylonitrile, toluene, molecular weight regulator, and polymerization initiator supplied by the pump. To the reaction vessel. The polymerization temperature of the second reaction vessel was 130 ° C, and the polymerization conversion rate was 75%. The copolymer solution obtained in the second reactor was directly devolatilized from the unreacted monomer and solvent using a twin-screw, three-stage vented extruder, and the intrinsic viscosity [r?] 0.48dlZg Of styrene-based resin A2-2.

[0089] (2-3) Production Example 3; Rubber-reinforced styrene-based resin

(2- 3-1) Production of rubbery polymer (A2-3a)

The stirrer and jacketed autoclave were dried and purged with nitrogen, and cyclohexane and 20 parts of butadiene were added. Next, n-butyl lithium was added, and isothermal polymerization was performed at 50 ° C. When the conversion rate reached 100%, 0.75 parts of tetrahydrofuran and 65 parts of butadiene were added, and polymerization was carried out at 50 ° C to 80 ° C. When the conversion rate reaches 100%, 15 parts of styrene is added, and the polymerization reaction is further carried out. A- B1-B2 triblock copolymerization before hydrogenation Got the body. The resulting block polymer comprises a butadiene block (Bl) having a styrene block (A) content of 15%, a butadiene block (B1) content of 65%, a butadiene block (B2) content of 20%, and a 1,2-bule content of 35%. It was a polymer with a number average molecular weight of 200,000 consisting of butadiene block (B2) force with a 1,2-bule content of 10%.

In a separate container, 1 part of titanocene dichloride was dispersed in cyclohexane and reacted with 0.5 part of triethylaluminum at room temperature. The obtained homogeneous solution was added to the above polymer solution and subjected to hydrogenation reaction at 50 ° C under a hydrogen pressure of 50 kgfZcm ² until the hydrogenation rate was almost 100% to obtain rubber polymer A2-3a. It was.

[0090] (2 3-2) Manufacture of rubber reinforced styrene resin (A2-3)

After substituting a stainless steel autoclave equipped with a ribbon blade with nitrogen, in a nitrogen stream, 28 parts (solid content) of the above polymer A2-3a previously made into a homogeneous solution using toluene as a solvent, 10.8 parts of styrene, Acrylonitrile (7.2 parts), methyl methacrylate (54 parts), toluene (120 parts), and tert-dodecyl mercaptan (0.1 part) were charged and heated with stirring. When the internal temperature reached 50 ° C, 0.5 parts of benzoyl peroxide and 0.1 part of dicumyl peroxide were added, and the temperature was further raised to 80 ° C. The polymerization reaction was carried out with constant control. After 6 hours from the start of the reaction, 1 hour was required, the temperature was raised to 120 ° C, and the reaction was further completed for 2 hours. The conversion was 97%.

After cooling to 100 ° C and adding 0.22 parts of 2,2-methylenebis 4 6-tert butylphenol, the reaction mixture is withdrawn from the autoclave, and unreacted substances and solvent are distilled off by steam distillation. The polymer was pelletized using an attached extruder to obtain polymer A2-3. The graft ratio of this product was 45%, and the intrinsic viscosity [r?] Of the acetone-soluble component was 0.45 dlZg.

[0091] (2-4) Production Example 4; rubber-reinforced styrene-based resin

Instead of rubber polymer A2-3a, 19 parts of ethylene / propylene rubber (trade name “EP84”, manufactured by JSR Corporation) is used, and 57 parts of styrene / acrylonitrile Z methyl methacrylate and acrylonitrile 24 instead of styrene / acrylonitrile. The polymerization reaction was carried out in the same manner as in Production Example 3, except that the ethylene / propylene rubber content was 20%, the graft ratio was 55%, and the acetone-soluble component had an intrinsic viscosity [7?] Of 0.45dlZg. A polymer A2-4 was obtained. [0092] (3) (A-3) Component

(3-1) Production Example 5: Partially Hydrogenated Styrene Butadiene Styrene Block Copolymer A stirrer and a jacketed autoclave were dried and purged with nitrogen, and a cyclohexane solution containing 30 parts of styrene was added. Next, n-butyllithium was added and polymerized at 70 ° C. for 1 hour, and then a cyclohexane solution containing 40 parts of butadiene was added for polymerization for 1 hour. Further, a cyclohexane solution containing 30 parts of styrene was added and polymerized for 1 hour. 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. . This had a styrene content of 60%, a 1,2-bule bond content of the polybutadiene portion of 35%, and a number average molecular weight of 74,000. 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 kgf / cm 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 polymer A3-1 having a hydrogenation rate of 69% in the butadiene part.

[0093] (3-2) Production Example 6: Completely hydrogenated styrene butadiene block copolymer

The stirrer and the jacketed autoclave were dried and purged with nitrogen, and cyclohexane and 20 parts of a solution of butane were added. Next, 0.025 part of n-butyllithium was added to conduct isothermal polymerization at 50 ° C. When the conversion rate reached 100%, 0.75 parts of tetrahydrofuran and 65 parts of butane were added, and polymerization was carried out at 50 ° C to 80 ° C. When the conversion reached 100%, 15 parts of styrene was added, and a polymerization reaction was further carried out to obtain an A-B1-B2 triblock copolymer before hydrogenation. As a result of sampling and analysis in the same manner as in Production Example 5, styrene block 15% (A block), 1,2-bula content 35% butadiene block (B1 block), 1,2 bull content 10% butadiene block (B2 block) It was a polymer having a number average molecular weight of 200,000.

In a separate container, 1 part of titanocene dichloride was dispersed in cyclohexane and reacted with 0.5 part of triethylaluminum at room temperature. The obtained homogeneous solution was added to the polymer solution, and a hydrogenation reaction was performed at 50 ° C. under a hydrogen pressure of 50 kgfZcm ² for 2 hours. As in Production Example 5, after adding 2, 6-di-tert-butylcatechol, the solvent was removed and the hydrogenation rate was approximately 100. % Hydrogenated polymer A3-2 was obtained.

[3-3] Production Example 7: Styrene Butadiene Styrene Block Copolymer

The autoclave with a stirrer and jacket was dried and purged with nitrogen, and 0.08 part of cyclohexane and tetrahydrofuran were added in a nitrogen stream. Thereafter, the temperature was raised, and when the internal temperature reached 70 ° C, a cyclohexane solution containing 0.052 parts of n-butyllithium was added, and then 15.5 parts of styrene was added and polymerized for 60 minutes ( 1st stage). Next, a mixture of 3 parts of styrene and 20 parts of butadiene was added and polymerized for 60 minutes (second stage). In addition, a mixture of 3 parts of styrene and 20 parts of butadiene was added and polymerized for 60 minutes (third stage). Further, a mixture of 3 parts of styrene and 20 parts of butadiene was added and polymerized for 60 minutes (fourth stage) to polymerize three tapered blocks. Next, 15.5 parts of styrene was polymerized for 60 minutes (5th stage). The polymerization conversion rate was 100%.

During the polymerization, the internal temperature was controlled to 70 ° C. After completion of the polymerization, as in Production Example 5, after adding 2,6-ditert-butylcatechol, the solvent was removed, and the block copolymer A3—having three tapered blocks where polystyrene gradually increased in the polybutadiene block part. Got 3. This had a number average molecular weight of 128,000 and a styrene content of 40%.

[3-4] Production Example 8; Styrene Butadiene Radial Teleblock Copolymer

The stirrer and jacketed autoclave were dried and purged with nitrogen, and 2.75 parts of cyclohexane and tetrahydrofuran were added in a nitrogen stream. After adding 25 parts of styrene and raising the temperature to 60 ° C., a cyclohexane solution containing 0.175 part of n-butyllithium was added, and the polymerization reaction was carried out for 60 minutes (first stage). Next, a mixture of 3 parts of styrene and 20 parts of butadiene was added to conduct a polymerization reaction for 60 minutes (second stage), and a mixture of 3 parts of styrene and 20 parts of butadiene was added to conduct a polymerization reaction for 60 minutes (3 In the second stage), 29 parts of butadiene was further added, and polymerization was completed until the conversion rate reached 100%. The coupling reaction was completed after adding 0.1 part of tetrachlorosilane as a coupling agent. After completion of the polymerization, 2,6-ditert-butylcatechol was added in the same manner as in Production Example 5, and then the solvent was removed to obtain a coupling type styrene-butadiene block copolymer A3-4 having a tapered block. . This had a styrene content of 31% and a number average molecular weight of 200,000.

[0096] (4) Component (A—4) The following polymer manufactured by Sanyo Chemical Industries, Ltd. was used as the component (A-4) of the present invention.

A4-1—Pelestat 230 (trade name; polyolefin-polyether block copolymer). A4-2—Pelestat 303 (trade name; polypropylene monopolyether block copolymer).

[0097] (5) Other ingredients;

The following were used as other components for improving antistatic properties.

D1; Nonionic antistatic agent; Kao's electro stripper TS-5 (trade name) Glycerin ester

D2; lithium trifluoromethanesulfonate; Sankonol AQ-75 manufactured by Sanko Chemical Industries

T (trade name) 75% aqueous solution of lithium trifluoromethanesulfonate

D3; Oxidized zinc whisker; Panatetra WZ-0501 made by Matsushita Electric Industrial Co., Ltd.

)

[0098] (5) The following polypropylene manufactured by Nippon Polypro Co., Ltd. was used as the component (B-1). The melt rate was measured at 230 ° C and 2.16 kg load according to JIS K7210: 1999.

Bl— 1; Novatec PP EA9BT (trade name)

Homotype, melt flow rate 0.5gZlO min

B1-2 — Novatec PP EG8 (trade name)

Random type, melt flow rate 0.8gZlO min

[0099] (6) The following polyethylene manufactured by Nippon Polyethylene Co., Ltd. was used as the component (B-2). The melt flow rate was measured in accordance with JIS K6922-2 at 190 ° C and 2.16 kg load.

B2— 1; Novatec LD LF122 (trade name)

Low density polyethylene, melt flow rate 0.3gZlO min

B2-2 — Novatec LD LF280H (trade name)

Low density polyethylene, melt flow rate 0.7gZlO min

B2-3; Novatec LD LF440HB (trade name)

Low density polyethylene, melt flow rate 2.8gZlO min

[0100] Examples 1 to 24, Comparative Examples 1 to 10

For component (A), each component was mixed with a Henschel mixer at the blending ratios shown in Tables 11 and 12, and then melt mixed using a twin-screw extruder (cylinder setting temperature 220 ° C). Kneaded and sprinkled with Pereztoy. After sufficiently drying the obtained pellets, the melt flow rate was measured by the above method using the pellets. The results are shown in Table 2.

Examples 1 to 20 and Comparative Example 1 to: In LO, using the above component (A) and the component (B) in Table 1-1 and Table 1-2, using a three-layer sheet extruder, the component (B) An intermediate layer and a three-layer sheet having (A) component as both surface layers (front and back of the intermediate layer) were obtained. In the production of the three-layer sheet, the temperature of the extruder was in the range of 190 ° C to 240 ° C.

The thickness of the three-layer sheet was 1 mm, the thickness of the intermediate layer was 0.8 mm, and the thicknesses of both surface layers were 0.1 mm. In addition, the (B-1) component and the (B-2) component of the intermediate layer were mixed in the composition shown in Table 1 and charged into an extruder of a three-layer extrusion apparatus.

Using this three-layer sheet, the antistatic property, chemical resistance, impact resistance, and sheet surface appearance were evaluated by the above-mentioned evaluation methods, and the evaluation results are shown in Table 2.

In addition, vacuum forming was performed using the above three-layer sheet (heater temperature 400 ° C, preheating time 20 to 45 seconds). The evaluation results are shown in Table 2.

In Examples 21 to 24, the above component (A) and the component (B) shown in Table 1-1 were used, and an azodicarbonamide-based foaming agent was further added to the component (B), and a multilayer T-die extruder was used. Using this, it was molded at 190 ° C, and a three-layer sheet with a total wall thickness of 3 mm was produced, with the expansion ratio of the intermediate layer being 2 and the thickness of both surface layers being 30 m.

Using this three-layer sheet, the antistatic property, chemical resistance, and sheet surface appearance were evaluated by the above evaluation methods, and the evaluation results are shown in Table 2.

[Table 1-1]

[Table 2]

From the results described in Table 2, the following is clear.

The multilayer sheets of Examples 1 to 20 of the present invention are excellent in antistatic property, chemical resistance, impact resistance, surface appearance and vacuum formability. In addition, the multilayer sheets of Examples 21 to 23 of the present invention are antistatic, Excellent chemical resistance and surface appearance.

Comparative Example 1 is an example in which the amount of the olefin resin (A-1) in the antistatic resin composition (A) of the present invention is small outside the scope of the invention, and the antistatic property, chemical resistance, Impact resistance, sheet surface appearance, and vacuum formability are poor. In Comparative Example 2, the blending amount of component (A-1) is outside the range of the invention. The blending amount of component (A-2), component (A-3), and component (A-4) is outside the range of the invention. This is a small example, and the antistatic and impact resistance is poor. Comparative Example 3 is an example in which the blending amount of the component (A-4) of the antistatic resin composition (A) of the present invention is small outside the scope of the invention, and the antistatic property is poor. Comparative Example 4 is an example in which the blending amount of component (A-4) is large outside the scope of the invention, and impact resistance and sheet surface appearance are poor. Comparative Example 5 is an example in which the amount of the (A-3) component of the antistatic resin composition (A) of the present invention is small outside the scope of the invention, and the impact resistance is poor. Comparative Example 6 is an example in which the amount of component (A-3) is large outside the scope of the invention, and the impact resistance and sheet surface appearance are poor. Comparative Example 7 is an example in which the melt flow rate of the component (B-1) of the polyolefin resin composition (B) of the present invention is high outside the scope of the invention, but the vacuum formability is poor. It was. Comparative Example 8 is an example in which the melt flow rate of the component (B-2) is high outside the scope of the invention. The force vacuum formability is inferior. In Comparative Example 9, the amount of the component (B-1) used outside the scope of the invention in the blending ratio of the olefin-based resin composition (B) of the present invention was large. This is a small example outside the range, and the vacuum formability is poor. In Comparative Example 10, the amount of (B-1) component used is small outside the scope of the invention, and the amount of (B-2) component used is outside the scope of the invention. Formability is inferior.

Industrial applicability

The multilayer sheet of the present invention has excellent anti-static properties, chemical resistance, impact resistance, surface appearance, and vacuum formability, which are unprecedented, and therefore requires high performance. '' It can be applied as various parts in the electronic field, the consumer electronics field, the sanitary field, etc.

Claims

The scope of the claims

[1] A multilayer sheet comprising at least a layer having the following component force (A) and a layer having the following component force (B).

(A) component: Olefin-based rosin (A-1) 7 to 91% by mass,

(A-1), (A-2) component, (A-3) and (A-4) components are 100% by mass in total).

Component (B): melt flow rate.: And (JIS K7210 1999, 230.C, 2. measured at 16kg load) force OgZlO min following polypropylene榭脂(B- 1) 60 to 97 weight ^_0/0, the melt Furore one Bok (JIS K6922- 2, 190.C, 2. measured at 16kg load) forces. OgZlO min following polyethylene emissions system榭脂(B- 2) Orefin system榭脂consisting 3-40 mass ^_0/0 Metropolitan Composition.

[2] The melt flow rate (JIS K7210: 1999, 230. C, measured at 2.16 kg load) of the component (A) is 1.0 to 15 gZlO. Multi-layer sheet.

[3] The multilayer sheet according to [1] or [2], wherein the polyolefin resin is a random copolymer of propylene and ethylene.

[4] The three-layer sheet in which the (B) component force layer is a core layer and the (A) component force layer is laminated on both the front and back surfaces of the core layer. The multilayer sheet according to any one of -3.

[5] The multilayer sheet according to any one of claims 1 to 4, which is obtained by a coextrusion molding method.

[6] The multilayer sheet according to any one of claims 1 to 5, which is formed by vacuum forming Molding.

[7] The multilayer sheet according to any one of [1] to [6], wherein the layer comprising the component (B) is foamed.

[8] The component (A) is the olefin-based resin (A-1) 7 to 30% by mass, the (co) polymer (A

2) Antistatic resin composition comprising 5 to 20% by mass, 15 to 50% by mass of the polymer (A-3), and 20 to 60% by mass of the block copolymer (A 4) (however, The multilayer sheet according to claim 7, wherein the total of (A-1) component, (A-2) component, (A-3) and (A-4) component is 100% by mass).