JP2007253614A - Multilayered sheet and formed product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a multilayered sheet excellent in anti-static property, chemical resistance, impact resistance, surface appearance and vacuum forming property. <P>SOLUTION: The multilayered sheet comprises a layer of the following constituent (A) and a layer of the following constituent (B). The constituent (A) is an anti-static resin composition comprising 7-91 mass% of an olefinic resin, 5-50 mass% of a rubber-modified styrene resin or a (co)polymer of the vinyl monomer, 2-50 mass% of a block copolymer containing a polymerized block of an aromatic vinyl compound and a polymerized block of a conjugated diene compound or its hydrogenated compound and 2-60 mass% of a block copolymer containing a polymerized olefinic block and a polymerized hydrophilic block. The constituent (B) is an olefinic resin composition comprising 60-97 mass% of a polypropylene resin having a melt flow rate of not greater than 2.0 g/10 min and 3-40 mass% of a polyethylene resin having a melt flow rate of not greater than 2.0 g/10 min. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  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.

  Polyolefin resins such as polypropylene are widely used in the electrical / electronic field, OA / home appliance field, vehicle field, sanitary field and the like because of their excellent chemical resistance, heat resistance, fluidity and the like. However, since this resin has a drawback that it is easily charged, various kinds of resins that are used or handled in static electricity, such as liquid crystal display devices, plasma displays, semiconductor peripheral members, clean rooms, etc. It was difficult to use for parts, sheets, films, etc. For the purpose of improving such drawbacks, Patent Documents 1 and 2 propose that a specific antistatic agent is blended, but there is no antistatic durability and antistatic properties are not sufficient. There was a problem such as. Moreover, as a method for maintaining antistatic properties, Patent Document 3 proposes that a specific polymer is blended with a polyolefin resin, but there is a problem that antistatic properties are not sufficiently exhibited.

On the other hand, rubber-reinforced styrene-based resins such as ABS resin are superior in mechanical strength such as impact resistance, moldability, rigidity, and the like, and also in the surface appearance of molded products. Therefore, electrical / electronic field, OA / home appliance field, vehicle field. Although it is widely used in the sanitary field, etc., the chemical resistance is not sufficient depending on the intended use, and further improvement in chemical resistance has been demanded. Further, these styrene 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 resin such as an ABS resin, but there is a problem that the antistatic property is not sufficiently exhibited.
From the above situation, as a result of intensive studies, a material having excellent antistatic properties can be obtained by blending a block copolymer having an olefin polymer block and a hydrophilic polymer block into a composition comprising a polyolefin resin and an ABS resin. A patent application was filed (Patent Document 5). However, a multilayer sheet using this material sometimes has insufficient vacuum formability.

JP-A-4-258647 JP 2000-313875 A Japanese Patent Laid-Open No. 2001-278985 Japanese Patent Laid-Open No. 60-23435 JP 2005-154730 A

  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 this multilayer sheet.

As a result of intensive studies to achieve the above object, the present inventors have a layer comprising a specific antistatic resin composition, and a composition containing a specific amount of a specific polypropylene resin and a specific polyethylene resin. It has been found that the object of the present invention can be achieved by laminating layers to form a multilayer sheet, and the present invention has been completed.
That is, according to the present invention, there is provided a multilayer sheet comprising at least a layer comprising the following component (A) and a layer comprising the following component (B).
(A) component: 7-91 mass% of olefin resin (A-1),
Rubber-reinforced styrene resin obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound in the presence of a rubber polymer, and / or a (co) polymer of the vinyl monomer (A -2) 5-50 mass%,
At least one polymer (A-3) selected from the group consisting of a block copolymer containing a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound and a hydrogenated product thereof ) 2-50 mass%,
2 to 60% by mass of a block copolymer (A-4) containing an olefin polymer block and a hydrophilic polymer block;
Containing an antistatic resin composition (however, the total of the components (A-1), (A-2), (A-3) and (A-4) is 100% by mass).
Component (B): Melt flow, with a melt flow rate (JIS K7210: 1999, measured at 230 ° C. under a load of 2.16 kg) of a polypropylene resin (B-1) having a content of 2.0 g / 10 min. An olefin resin composition comprising 3 to 40% by mass of a polyethylene resin (B-2) having a rate (measured at JIS K6922-2, 190 ° C., 2.16 kg load) of 2.0 g / 10 min or less.
The layer composed of the component (B) may be foamed. When a foam laminated sheet having a high antistatic property and a smooth surface and an excellent surface appearance of the sheet is required, the component (A) is 7 to 30% by mass of the olefin resin (A-1), 5-20% by mass of the (co) polymer (A-2), 15-50% by mass of the polymer (A-3), and 20-60% by mass of the block copolymer (A-4). The antistatic resin composition (however, the total of the components (A-1), (A-2), (A-3) and (A-4) is 100% by mass)).
According to another aspect of the present invention, there is provided a molded product obtained by vacuum-forming the multilayer sheet.

  The present invention constitutes a multilayer sheet from a layer composed of the specific antistatic resin composition and a layer composed of a polypropylene resin having the specific melt flow rate and an olefin resin composition composed of a polyethylene resin. Therefore, a sheet excellent in antistatic property, chemical resistance, impact resistance, surface appearance, and vacuum formability can be obtained, and by vacuum forming this multilayer sheet, the above-mentioned various characteristics are excellent. A molded product can be obtained.

The present invention will be described in detail below. In the present specification, “(co) polymerization” means homopolymerization and copolymerization, “(meth) acryl” means acryl and / or methacryl, and “(meth) acrylate” Means acrylate and / or methacrylate.

The olefin-based resin (A-1) related to the antistatic resin composition (A) of the present invention is an olefin-based resin composed of at least one olefin having 2 to 10 carbon atoms, and the component (A- (Co) polymers excluding 4). This olefin resin (A-1) can be used individually by 1 type or in combination of 2 or more types.
Examples of olefins used for forming the olefin resin (A-1) include ethylene and propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, 3 -Α-olefins such as methylhexene-1 and cyclic olefins such as norbornene. These can be used individually by 1 type or in combination of 2 or more types. Of these, ethylene, propylene, butene-1, 3-methylbutene-1, 4-methylpentene-1, and norbornene are preferable.
Other monomers that can be used as necessary in the formation of the olefin resin (A-1) include 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and 7-methyl. Non-conjugated dienes such as -1,6-octadiene, 1,9-decadiene and the like can be mentioned.

As the olefin resin (A-1), a polymer mainly containing a propylene unit such as polypropylene and a propylene / ethylene copolymer, a polyethylene, and an ethylene / norbornene copolymer are preferable, and a polypropylene, a propylene / ethylene copolymer are particularly preferable. It is a polymer mainly containing a propylene unit such as a coalescence. These may be used alone or in combination. The propylene / ethylene copolymer is preferably a random copolymer, a block copolymer or the like, and it is particularly preferable to use a random type in view of the sheet surface appearance when it is formed into a multilayer sheet. As the polyethylene, any of high density polyethylene, low density polyethylene, linear low density polyethylene and the like can be used.
As the olefin 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 metallocene catalyst polymerization method.
Furthermore, as the olefin resin used in the present invention, one obtained by decatalyzing a polymerization catalyst or one modified with an acid anhydride, a carboxyl group, an epoxy group or the like can be used.

It does not matter whether the olefin resin (A-1) has crystallinity, but it is preferable to use at least one of those having a crystallinity by X-ray diffraction of 10% or more at room temperature.
Moreover, it is preferable to use at least 1 sort (s) whose melting | fusing point measured based on JISK7121 of olefin resin (A-1) is 40 degreeC or more.
When a 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: 1999 is preferably 0.01 to 500 g / 10. Min, more preferably 0.05 to 100 g / 10 min. When a polyethylene resin is used, the melt flow rate measured according to JIS K6922-2 is preferably 0.01 to 500 g / 10 min. More preferably, it is 0.05-100 g / 10min.

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

The component (A-2) of the present invention comprises a rubber-reinforced styrene resin obtained by polymerizing a vinyl monomer (b) containing an aromatic vinyl compound in the presence of the rubber polymer (a), and / Or (co) polymer of the vinyl monomer (b). The latter (co) polymer is obtained by polymerizing the vinyl monomer (b) containing an aromatic vinyl compound in the absence of the rubbery polymer (a).
The component (A-2) of the present invention contains at least one polymer obtained by graft polymerization of the vinyl monomer (b) in the presence of the rubbery polymer (a) in terms of impact resistance. Is preferred. The content of the rubber 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.

The rubbery polymer (a) is not particularly limited, but polybutadiene, butadiene / styrene copolymer, butadiene / acrylonitrile copolymer, ethylene / propylene copolymer, ethylene / propylene / nonconjugated diene copolymer, Examples include ethylene / butene-1 copolymer, ethylene / butene-1 / non-conjugated diene copolymer, acrylic rubber, silicone rubber, silicone / acrylic IPN rubber, and the following component (A-3). One species can be used alone, or two or more species can be used in combination.
Of these, polybutadiene, butadiene / styrene copolymer, ethylene / propylene copolymer, ethylene / propylene / nonconjugated diene 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.

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 40 to 98. % By 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. That is, 1 g of a rubbery polymer 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 W ₁ gram) were heated at 80 ° C. for 6 hours. It vacuum-drys, weighs (it is set as ₂ mass of mass W), and calculates by following formula (1).

Gel content (% by mass) = [{W ₂ (g) −W ₁ (g)} / 1 (g)] × 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 and the like during the production of the rubbery polymer.

  Examples of the aromatic vinyl compound constituting the vinyl monomer (b) include styrene, α-methylstyrene, hydroxystyrene, and the like. These may be used alone or in combination of two or more. Can do. Of these, styrene and α-methylstyrene are preferred.

  Examples of other vinyl monomers copolymerizable with the aromatic vinyl compound include vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, and other various functional group-containing unsaturated compounds. Preferably, the vinyl monomer (b) comprises an aromatic vinyl compound as an essential monomer component, and, if necessary, a group consisting of a vinyl cyanide compound, a (meth) acrylic acid ester compound and a maleimide compound. One or more selected from the above are used in combination as a monomer component, and if necessary, at least one of other various functional group-containing unsaturated compounds is used in combination as a monomer component. As other various functional group-containing unsaturated compounds, 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 other various functional group-containing unsaturated compounds can be used alone or in combination of two or more.

Examples of the vinyl cyanide compound used here include acrylonitrile, methacrylonitrile and the like, and these can be used alone or in combination of two or more. When a vinyl cyanide compound is used, chemical resistance is imparted. When using a vinyl cyanide compound, the usage-amount is in the (b) component, Preferably it is 1-60 mass%, More preferably, it is 5-50 mass%.
Examples of (meth) acrylic acid ester compounds include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like. These may be used alone or in combination of two or more. Can be used in combination.
Use of a (meth) acrylic acid ester compound is preferable because surface hardness is improved. When using a (meth) acrylic acid ester compound, the usage-amount is in the (b) component, Preferably it is 1-80 mass%, More preferably, it is 5-80 mass%.
Examples of maleimide compounds include maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and the like. 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 post-imidized. When a maleimide compound is used, heat resistance is imparted. When using a maleimide compound, the amount used thereof is preferably 1 to 60% by mass, more preferably 5 to 50% by mass in the component (b).

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

Examples of the hydroxyl group-containing unsaturated compound include 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, and 3-hydroxy-2- Examples include methyl-1-propene, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, N- (4-hydroxyphenyl) maleimide, and these may be used alone or in combination of two or more. it can.
Examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline and the like, and these 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-vinyldiethylamine, N-acetylvinylamine, and acrylamine. , Methacrylamine, N-methylacrylamine, acrylamide, N-methylacrylamide, p-aminostyrene and the like, and these can be used alone or in combination of two or more.
When the above-mentioned various other functional group-containing unsaturated compounds are used, when the styrenic resin and another polymer are blended, the compatibility between them may be improved. Preferred monomers for achieving such effects 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 the component (A-2), and is 0. 1-20 mass% is preferable and 0.1-10 mass% is further 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 monomers constituting the vinyl monomer (b) are styrene / acrylonitrile, styrene / methyl methacrylate, styrene / acrylonitrile / methyl methacrylate, styrene / acrylonitrile / glycidyl methacrylate, styrene / acrylonitrile / 2. -Hydroxyethyl methacrylate, styrene / acrylonitrile / (meth) acrylic acid, styrene / N-phenylmaleimide, styrene / methyl methacrylate / cyclohexylmaleimide and the like, and particularly preferred combinations are styrene / acrylonitrile, rubbery polymer ( More preferred combinations of monomers polymerized in the presence of a) are styrene / acrylonitrile = 65/45 to 90/10 (mass ratio), styrene / methyl methacrylate = 80/2. ~ 20/80 (mass ratio), styrene / acrylonitrile / methyl methacrylate, the amount of styrene is 20 to 80% by mass, and the total of acrylonitrile and methyl methacrylate is in the range of 20 to 80% by mass, especially Styrene / acrylonitrile is preferably 70/30 to 85/15 (mass ratio).

  The component (A-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 of 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, a preferred polymerization method of the polymer obtained by (co) polymerizing the vinyl monomer (b) in the absence of the rubbery polymer (a) is bulk polymerization, solution polymerization, suspension polymerization, And emulsion polymerization.

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.
Examples of the polymerization initiator include cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, tetramethylbutyl hydroperoxide, tert-butyl hydroperoxide, potassium persulfate, azobisisobutyronitrile and the like. Can be mentioned.
Moreover, there are various reducing agents, sugar-containing iron pyrophosphate formulations, sulfoxylate formulations 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, n-hexyl mercaptan, terpinolene, and α-methylstyrene dimer.
Emulsifiers 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, rosin acid A rosin acid salt such as potassium can be used.

  In the emulsion polymerization, the rubber polymer (a) and the vinyl monomer (b) are used by adding the vinyl monomer (b) in the presence of the total amount of the rubber polymer (a). May be polymerized, or may be polymerized by dividing or continuously adding. Moreover, you may add a part of rubber-like polymer (a) in the middle of superposition | polymerization.

  After the emulsion polymerization, the obtained latex is usually coagulated with a coagulant, washed with water and dried to obtain the component powder (A-2) 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, citric acid and malic acid can be used.

The solvent that can be used in the case of producing the component (A-2) by solution polymerization is an inert polymerization solvent used in ordinary radical polymerization, for example, aromatic hydrocarbons such as ethylbenzene and toluene, methyl ethyl ketone, Examples include ketones such as acetone, acetonitrile, dimethylformamide, N-methylpyrrolidone, and the like.
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, diacyl peroxide, peroxy ester, hydroperoxide, azobisisobutyronitrile, benzoyl peroxide, 1,1′-azobis ( Cyclohexane-1-carbonitrile) and the like are preferably used.
When a chain transfer agent is used, for example, mercaptans, terpinolenes, α-methylstyrene dimers, etc. can be used.
Moreover, when manufacturing by block polymerization and suspension polymerization, the polymerization initiator, chain transfer agent, etc. which were demonstrated in solution polymerization can be used.
The amount of monomer remaining in the component (A-2) obtained by the above polymerization methods is preferably 10,000 ppm or less, more preferably 5,000 ppm or less.

The polymer component obtained by polymerizing the vinyl monomer (b) in the presence of the rubber polymer (a) usually contains the rubber monomer (b). a) a copolymer obtained by graft copolymerization and an ungrafted component [(co) polymer of the above-mentioned vinyl monomer (b)] that is not grafted on the rubber polymer.
The graft ratio of the component (A-2) is preferably 20 to 200% by mass, more preferably 30 to 150% by mass, particularly preferably 40 to 120% by mass, and the graft rate is represented by the following formula (2). Can be sought.

Graft ratio (mass%) = {(TS) / S} × 100 (2)
In the above formula (2), T represents (A-2) 1 g of the component is added to 20 ml of acetone (but acetonitrile when the rubbery polymer (a) is an acrylic rubber) and shaken. The mass (g) of insoluble matter obtained by shaking for 2 hours and then centrifuging for 60 minutes with a centrifuge (rotation speed: 23,000 rpm) to separate the insoluble matter and the soluble matter. Is the mass (g) of the rubbery polymer contained in 1 g of component (A-2).

In addition, the intrinsic viscosity of the component (A-2) related to the present invention (however, when the rubbery polymer (a) is an acrylic rubber, acetonitrile) is soluble in intrinsic viscosity [η] (as a solvent (Measured at 30 ° C. using methyl ethyl ketone) is preferably 0.2 to 1.2 dl / g, more preferably 0.2 to 1.0 dl / g, particularly preferably 0.3 to 0.8 dl / g. is there.
The average particle size of the grafted rubber-like polymer particles dispersed in the component (A-2) according to the present invention is preferably 500 to 30,000, more preferably 1,000 to 20,000, and particularly preferably It is in the range of 1,500 to 8,000cm. The average particle diameter can be measured by a known method using an electron microscope.

  The amount of the component (A-2) constituting the component (A) of the present invention is the components (A-1), (A-2), (A-3), and (A-4) of the present invention. ) 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 in the total 100% by mass of the components, and has high antistatic properties. When a foam laminate sheet having a smooth surface and an excellent surface appearance 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 inferior, and if it exceeds 50% by mass, the chemical resistance is inferior.

  The component (A-3) of the present invention contains a polymer block (A-3-1) mainly composed of an aromatic vinyl compound and a polymer block (A-3-2) mainly composed of a conjugated diene compound. It is at least one polymer selected from the group consisting of a copolymer (A-3-a) and a hydrogenated product (A-3-b) thereof.

Examples of the aromatic vinyl compound used herein include styrene, α-methylstyrene, hydroxystyrene, and the like, preferably styrene and α-methylstyrene, and particularly preferably styrene.
Examples of the conjugated diene compound include butadiene, isoprene, hexadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and preferably butadiene and isoprene. These can be used individually by 1 type or in combination of 2 or more types. Further, the block (A-3-2) may be a block in which two or more conjugated diene compounds are used and bonded in any form of random, block, and taper. Moreover, (A-3-2) may contain 1 to 10 taper blocks in which the aromatic vinyl compound gradually increases, and the conjugated diene compound of the polymer block (A-3-2) The derived polymer blocks having different vinyl bond contents may be appropriately copolymerized.

A preferred structure of the component (A-3) of the present invention is a polymer represented by the following formulas (I) to (III) or a hydrogenated product thereof.
(AB) _Y ... (I)
(AB) _Y- X (II)
A- (B-A) _Z (III)
(In the structural formulas (I) to (III), A is a polymer block mainly composed of an aromatic vinyl compound. If the polymer block is substantially composed of an aromatic vinyl compound, a part of the conjugated diene compound is included. Preferably, it is a polymer block containing 90% by mass or more, more preferably 99% by mass or more of an aromatic vinyl compound, B is a homopolymer of a conjugated diene compound or an aromatic vinyl compound, etc. And X is a residue of the coupling agent, Y is an integer of 1 to 5, and Z is an integer of 1 to 5.)

  In the component (A-3) of the present invention, the use ratio of the aromatic vinyl compound and the conjugated diene compound is preferably within the range of aromatic vinyl compound / conjugated diene compound = 10 to 70/30 to 90% by mass, and more preferably. It is 15-65 / 35-85 mass%, Most preferably, it is the range of 20-60 / 40-80 mass%.

  The block copolymer composed of an aromatic vinyl compound and a conjugated diene compound is known in the technical field of anionic polymerization, for example, Japanese Patent Publication No. 47-28915, Japanese Patent Publication No. 47-3252, Japanese Patent Publication No. 48-2423. And the Japanese Patent Publication No. 48-20038. A method for producing a polymer block having a tapered block is disclosed in JP-A-60-81217.

  The vinyl bond content (1,2- and 3,4-bond) content derived from the conjugated diene compound of the component (A-3) of the present invention is preferably in the range of 5 to 80%. The number average molecular weight of the component A-3) is preferably 10,000 to 1,000,000, more preferably 20,000 to 500,000, and particularly preferably 20,000 to 200,000. Among these, the number average molecular weight of the A part represented by the above (I) to (III) is preferably in the range of 3,000 to 150,000, and the number average molecular weight of the B part is in the range of 5,000 to 200,000. .

Adjustment of the vinyl bond amount of the conjugated diene compound is performed by adjusting amines such as N, N, N ′, N′-tetramethylethylenediamine, trimethylamine, triethylamine, diazocyclo (2,2,2) octamine, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diester. It can be carried out using ethers such as butyl ether, thioethers, phosphines, phosphoamides, alkylbenzene sulfonates, alkoxides of potassium and sodium, and the like.
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 is also preferably included in the component (A-3) of the present invention. As coupling agents used here, diethyl adipate, divinylbenzene, methyldichlorosilane, silicon tetrachloride, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, dimethylchlorosilicon, tetrachlorogermanium, 1, Examples include 2-dibromoethane, 1,4-chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized linseed oil, tolylene diisocyanate, 1,2,4-benzene triisocyanate, and the like.

  Among the above block copolymers, preferred from the viewpoint of impact resistance is a polymer having 1 to 10 taper blocks in which the aromatic vinyl compound gradually increases in the block (A-3-2), and / or Alternatively, it is of a radial block type that has been coupled.

  Further, as the component (A-3), the block copolymer itself can be used, or one obtained by partially or completely hydrogenating the carbon-carbon double bond of the conjugated diene moiety can be used. From the low temperature impact property of the obtained composition, it is preferable to use a non-hydrogenated one or a hydrogenation rate of less than 90%. From the aspect of the weather resistance (light) of the obtained composition, It is preferable to use a hydrogenated product of 90% or more.

  The hydrogenation reaction of the block copolymer containing the polymer block mainly composed of the aromatic vinyl compound and the polymer block mainly composed of the conjugated diene compound obtained by the above method can be carried out by a known method. The desired 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, JP-A-1 There is a method disclosed in Japanese Patent No. 297413.

The block copolymer (A-3-a) and the hydrogenated product (A-3-b) thereof are composed of other block polymers and / or graft polymers (provided that the component (A-2) above). May be chemically bonded.
100% by mass of the block copolymer (A-3-a) and the other polymer chemically bonded to the hydrogenated product (A-3-b) must be chemically bonded. The object of the present invention can be achieved if at least 10% by mass of the other polymer is chemically bonded.

  Preferred as the block copolymer (A-3-a) and the other polymer bonded to the hydrogenated product (A-3-b) as a block polymerization are aromatic polycarbonate and / or polyurethane, More preferably, it is an aromatic polycarbonate. An aromatic polycarbonate block copolymer mixture can be manufactured by the method of Unexamined-Japanese-Patent No. 2001-220506, for example. Furthermore, TM-S4L77, TM-H4L77 (trade name) of TM polymer series manufactured by Kuraray Co., Ltd. can be obtained.

  A particularly preferred method for graft polymerizing the other polymer to the block copolymer (A-3-a) and the hydrogenated product (A-3-b) thereof is the block copolymer (A- In this method, a vinyl monomer is graft-polymerized in the presence of 3-a) and a hydrogenated product (A-3-b) thereof. As the vinyl monomer, the vinyl monomer (b) as the component (A-2) (however, it may be the same as that used in the component (A-2) or may not be the same) is preferable. used. As the method for graft polymerization, the emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization and the like described above for the component (A-2) can be used, more preferably solution polymerization and bulk polymerization.

  The component (A-3) of the present invention is 2 to 2 in 100% by mass in total of the components (A-1), (A-2), (A-3) and (A-4) of the present invention. 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 excellent smoothness on the sheet surface. When a foamed laminated sheet is required, it is preferably 15 to 50% by mass. If it is less than 2% by mass, the impact resistance is inferior. If it exceeds 50% by mass, the impact resistance and the sheet surface appearance are inferior.

  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), and may be a diblock. However, it may be a multi-block of a tri-block or more. The olefin polymer block (A-4-1) is a (co) polymer of olefins. Examples of olefins used herein include ethylene and α-olefins such as propylene, butene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, 3-methylhexene-1 and the like. Furthermore, there are cyclic olefins such as norbornene, preferably ethylene, propylene, butene-1, 3-methylbutene-1, 4-methylpentene-1, and norbornene. In addition, non-conjugated dienes such as 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 1,9-decadiene and the like are used as one of the polymer components. Can be used as a part. The polystyrene-reduced number average molecular weight of the olefin polymer block (A-4-1) by gel permeation chromatography (GPC) is preferably 800 to 20,000, more preferably 1,000 to 10,000, especially. Preferably it is 1,2000-6,000.

The block (A-4-1) is chemically bonded to the block (A-4-2), and the bond is selected from an ester bond, an amide bond, an ether bond, a urethane bond, an imide bond, and the like. It has at least one type of bond, and has a structure in which the bonds are alternately and alternately bonded through these bonds. However, unbound blocks may be included within a range that does not affect the antistatic property described later.
Therefore, the molecular end of the block (A-4-1) needs to be modified with a functional group having reactivity with the functional groups at both ends of the block (A-4-2). These functional groups include carboxylic acid groups, hydroxyl groups, amino groups, acid anhydride groups, oxazoline groups, epoxy groups and the like.
A preferable method for imparting these functional groups is a carbon-carbon having the above-described functional group in the component (A-4-1) having a carbon-carbon double bond at the molecular end obtained by a thermal degradation method. In this method, an unsaturated compound is added.

Examples of the hydrophilic polymer of the block (A-4-2) component include polyethers, polyether-containing hydrophilic polymers, and anionic polymers.
Examples of the polyether include polyether diol, polyether diamine, and modified products thereof.
The polyether-containing hydrophilic polymer includes a polyether ester amide having a polyether diol segment, a polyether amide imide having a polyether diol segment, a polyether ester having a polyether diol segment, and a polyether diamine segment. And polyether urethane having a segment of polyether diol or polyether diamine.
As the anionic polymer, an anionic polymer having a sulfonyl group-containing dicarboxylic acid and the above polyether as essential component units and preferably having 2 to 80, more preferably 3 to 60 sulfonyl groups in one molecule. Is raised. These may be linear or branched. Particularly preferred component (A-4-2) is a polyether.

Among the polyethers, the polyether diol has the general formula (IV):
H— (OA ¹ ) _{n —OE} ¹ —O (A ¹ O) _{n ′} —H,
And general formula (V): H— (OA ² ) _m —O—E ² —O— (A ² O) _{m ′} —H. 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, and n and n ′ are hydroxyl groups of the divalent hydroxyl group-containing compound. This represents the number of alkylene oxide additions per unit. n (OA ¹ ) and n ′ (A ¹ O) may be the same or different, and the bond form when these are composed of two or more oxyalkylene groups is Either block or random or a combination thereof may be used. n and n ′ are integers of usually 1 to 300, preferably 2 to 250, particularly preferably 10 to 100. N and n ′ may be the same or different.

Examples of the divalent hydroxyl group-containing compound include compounds containing two alcoholic or phenolic hydroxyl groups in one molecule, that is, dihydroxy compounds. Specifically, divalent alcohols (for example, having 2 to 12 carbon atoms) Aliphatic, alicyclic, or aromatic dihydric alcohols), C6-C18 dihydric phenols, and tertiary amino group-containing diols.
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 the alicyclic dihydric alcohol include 1,2- and 1,3-cyclopentanediol, 1,2-, 1,3- and 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. Examples of the aromatic dihydric alcohol include xylene diol.
Dihydric phenols include monocyclic dihydric phenols such as hydroquinone, catechol, resorcin, urushiol, bisphenol A, bisphenol F, bisphenol S, 4,4'-dihydroxydiphenyl-2,2-butane, dihydroxybiphenyl, dihydroxydiphenyl ether And condensed polycyclic dihydric phenols such as dihydroxynaphthalene and binaphthol.

In the general formula (V), E ² is a residue obtained by removing the hydroxyl group from the divalent hydroxyl group-containing compound described in the general formula (IV), and A ² is at least partially represented by the general formula (VI): —CHR— CHR ′ — [wherein one of R and R ′ is a group represented by the general formula (VII): —CH ₂ O (A ³ O) _X R ″, and the other is H. In general formula (VII), x is an integer of 1 to 10, R ″ is H or a C 1-10 alkyl group, aryl group, alkylaryl group, arylalkyl group or acyl, A ³ is carbon number 2 to 4 alkylene groups. And the remainder may be an alkylene group having 2 to 4 carbon atoms. The m (OA ² ) and m ′ (A ² O) may be the same or different. m and m ′ are preferably integers of 1 to 300, more preferably 2 to 250, and particularly preferably 10 to 100. M and m ′ may be the same or different.

  The polyether diol represented by the general formula (IV) can be produced by addition reaction of an alkylene oxide with a divalent hydroxyl group-containing compound. Examples of the alkylene oxide 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 kinds of alkylene oxide are used in combination, the bonding form may be random and / or block. Preferable examples of the alkylene oxide include ethylene oxide alone and block and / or random addition using ethylene oxide in combination with other alkylene oxides. The number of alkylene oxides added is preferably an integer of 1 to 300, more preferably 2 to 250, and particularly preferably 10 to 100 per hydroxyl group of the divalent hydroxyl group-containing compound.

  Preferred methods for producing the polyether diol represented by the general formula (V) include the following methods (a) and (b).

  (A) General formula (VIII):

［一般式（VIII）中のＡ^４は炭素数２〜４のアルキレン基、ｐは１〜１０の整数、Ｒ^１はＨまたは炭素数１〜１０のアルキル基、アリール基、アルキルアリール基、アリールアルキル基またはアシル基である。］
で表されるグリシジルエーテルを重合、または炭素数２〜４のアルキレンオキサイドと共重合する方法。

^{[A 4} in the general formula (VIII) is an alkylene group having 2 to 4 carbon atoms, p is an integer of from 1 to 10, ^{R 1} is H or an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, an aryl An alkyl group or an acyl group; ]
The method of superposing | polymerizing the glycidyl ether represented by these, or copolymerizing with a C2-C4 alkylene oxide.

(A) A method of using a divalent hydroxyl group-containing compound as a starting material and passing through a polyether having a chloromethyl group in the side chain. More specifically, epichlorohydrin or epichlorohydrin and alkylene oxide are added and copolymerized to obtain a polyether having a chloromethyl group in the side chain, and then the polyether, a polyalkylene glycol having 2 to 4 carbon atoms and R ^1. X (R ¹ is as described above, X is Cl, Br or I) is reacted in the presence of an alkali, or the polyether is reacted with a polyalkylene glycol monocarbyl ether having 2 to 4 carbon atoms in the presence of an alkali. Is the method.

As the alkylene oxide having 2 to 4 carbon atoms used here, all of those described above can be used.
The preferred component (A-4) of the present invention is obtained by polymerizing the olefin polymer block (A-4-1) and the hydrophilic polymer block (A-4-2) by a known method. Can do. 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. A known polymerization catalyst can be used in the polymerization reaction.

  In addition, known polymerization catalysts can be used in the polymerization reaction, but preferred are tin-based catalysts such as monobutyltin oxide, antimony-based catalysts such as antimony trioxide and antimony dioxide, and titanium-based catalysts such as tetrabutyl titanate. , Zirconium hydroxide, zirconium oxide, zirconium acetate such as zirconyl acetate, or a combination of two or more selected from group IIB organic acid salt catalysts.

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 / or an alkaline earth metal salt (C). These components can be contained before the polymerization of the component (A-4), during the polymerization of the component (A-4), or after the polymerization of the component (A-4). Moreover, this component (C) may be mix | blended when manufacturing the antistatic resin composition of this invention, and can also be contained by the method combined with said method.
Examples of the component (C) include organic acids, sulfonic acids, inorganic acid salts, halides and the like of alkali metals such as lithium, sodium and potassium and / or alkaline earth metals such as magnesium and calcium.

Specific preferred examples of the component (C) include halides of alkali metals such as lithium chloride, sodium chloride, potassium chloride, lithium bromide, sodium bromide, potassium bromide; lithium perchlorate, sodium perchlorate, Inorganic acid salts of alkali metals such as potassium perchlorate,
Organic acid salts of alkali metals such as potassium acetate and lithium stearate; carbons of alkyl groups such as octyl sulfonic acid, dodecyl sulfonic acid, tetradecyl sulfonic acid, stearyl sulfonic acid, tetracosyl sulfonic acid, 2-ethylhexyl sulfonic acid Alkali metal salts of alkyl sulfonic acids having a number of 8 to 24; alkali metal salts of aromatic sulfonic acids such as phenyl sulfonic acid and naphthyl sulfonic acid; octyl phenyl sulfonic acid, dodecyl phenyl sulfonic acid, dibutyl phenyl sulfonic acid, dinonyl phenyl Alkali metal salts of alkylbenzene sulfonic acid having 6 to 18 carbon atoms in the alkyl group such as sulfonic acid; dimethyl naphthyl sulfonic acid, diisopropyl naphthyl sulfonic acid, dibutyl naphthyl sulfonic acid, etc. having 2 to 18 carbon atoms in the alkyl group Al Examples include alkali metal salts such as lunaphthalene sulfonic acid; alkali metal salts such as fluorinated sulfonic acid such as trifluoromethane sulfonic acid, and the like. These can be used alone or in combination of two or more. . The component (C) can be used in an amount of preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass with respect to the component (A-4) of the present invention.

The preferred ratio of the (A-4-1) component / (A-4-2) component in the (A-4) component of the present invention is in the range of 10-90 / 10-90% by mass, more preferably 20 It is -80 / 20-80 mass%, Most preferably, it is the range of 30-70 / 30-70 mass%.
Such a block copolymer (A-4) can be produced by, for example, the methods described in JP-A Nos. 2001-278985 and 2003-48990, and further the (A -4) The component can be obtained as 300, 303 of Pelestat 300 series manufactured by Sanyo Chemical Industries, Ltd., 230, 201, etc. of 200 series.

  The component (A-4) of the present invention is 2 to 60 in a total of 100% by mass of the component (A-1), the component (A-2), the component (A-3), and the component (A-4). % 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 (A-4) of the present invention comprises the components (A-1), (A-2), (A-3), And (A-4) in a total of 100% by mass, preferably 2 to 40% by mass, more preferably 3 to 35% by mass, still more preferably 5 to 35% by mass, and particularly preferably 5 to 30% by mass. . In applications where excellent antistatic properties are required, the component (A-4) of the present invention includes (A-1) component, (A-2) component, (A-3) component, and (A-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.

   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 the component (A) of the present invention is in the range of 0.5 to 25 g / 10 min. Preferably, it is 0.5 to 20 g / 10 min, and particularly preferably 1.0 to 15 g / 10 min. When 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 arbitrarily changed by changing the molecular weight, blending amount, etc. of the component (A-1), the component (A-2), the component (A-3), or the component (A-4). You can change it.

The olefin resin composition of component (B) of the present invention is a polypropylene resin (B-1) having a melt flow rate (measured at JIS K7210: 1999, 230 ° C., 2.16 kg load) of 2.0 g / 10 min or less. ) And a polyethylene resin (B-2) having a melt flow rate (measured at JIS K6922-2, 190 ° C., 2.16 kg load) of 2.0 g / 10 min or less.
Examples of the polypropylene resin (B-1) used here include a propylene homopolymer and a copolymer of propylene and another monomer, and the other monomer used here is ethylene. , Butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, 3-methylhexene-1, etc., particularly preferably ethylene.
Examples of the propylene / ethylene copolymer include a random copolymer and a block copolymer, and any of them can be used. The amount of the monomer other than propylene constituting the polypropylene resin (B-1) is preferably 0 to 60% by mass of the entire polypropylene resin (B-1).
As the polypropylene resin of the component (B-1) used in the present invention, homopolypropylene is particularly preferable.

(B-1) The melt flow rate measured by 230 degreeC and the 2.16kg load according to JISK7210: 1999 of a component is 2.0 g / 10min or less, Preferably it is 0.05-1.5 g / 10min. More preferably, it is 0.1-1.4 g / 10min, Most preferably, it is 0.3-1.0g / 10min. When it exceeds 2.0 g / 10 minutes, the vacuum formability of the multilayer sheet of the present invention is inferior.

As the polyethylene resin (B-2) used in the present invention, there are a homopolymer of ethylene and a copolymer of ethylene and another monomer. , Butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, 3-methylhexene-1, norbornene, and the like.
The polyethylene resin used in the present invention is particularly preferably an ethylene homopolymer. As the polyethylene, any of high-density polyethylene, low-density polyethylene, and linear low-density polyethylene can be used, but low-density polyethylene is particularly preferable from the viewpoint of vacuum moldability.

The melt flow rate measured at 190 ° C. under a load of 2.16 kg according to JIS K6922-2 of the component (B-2) is 2.0 g / 10 min or less, preferably 0.05 to 1.5 g / 10 min. More preferably, it is 0.1-1.2 g / 10min, Most preferably, it is 0.3-1.0g / 10min. When it exceeds 2.0 g / 10 minutes, the vacuum formability of the multilayer sheet of the present invention is inferior.

The olefin resin composition (B) of the present invention comprises a component (B-1) and a component (B-2), and the amount used thereof is (B-1) component / (B-2) component = 60 to. 97/3 to 40% by mass, preferably 70 to 95/5 to 30% by mass, more preferably 70 to 90/10 to 30% by mass, particularly preferably 75 to 90/10 to 25% by mass, In the region where the component (B-1) is less than 60% by mass and the component (B-2) exceeds 40% by mass, the sheet appearance and the vacuum formability are inferior. Further, when the component (B-1) exceeds 97% by mass and the component (B-2) is less than 3% by mass, the vacuum formability is inferior.

For the purpose of improving the antistatic property of the component (A) of the present invention, a specific compound can also be blended during the production of the component (A). Examples of the specific compound used here include lithium salt compounds and nonionic compounds. System antistatic agents are preferred.
As the lithium salt compound, lithium perchlorate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide, tris (trifluoromethanesulfonyl) methane lithium and the like are preferably used, and more preferably lithium trifluoromethanesulfonate. is there. These can be used individually by 1 type or in combination of 2 or more types. These can be obtained as a solution or a master batch as Sankonol 0862-13T, AQ-50T, AQ-75T, or TBX-25 (trade name) manufactured by Sanko Chemical Co., Ltd. This lithium salt compound can also be used as the component (C).

  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 by mass, and particularly preferably 0 with respect to 100 parts by mass of the component (A) of the present invention. Used in the range of 3 to 2 parts by mass. If the amount used is less than 0.01 parts by mass, the effect of improving antistatic properties cannot be obtained, and if it exceeds 5 parts by mass, the impact resistance tends to decrease.

  Nonionic antistatic agents include polyhydric alcohol ester compounds, amines, amides, etc., and polyhydric alcohol ester compounds include glycerin monostearate, glycerin monomyristate, glycerin monopalmitate, glycerin monostearate. Rate, glycerol monobehenate, glycerol monooleate, diglycerol monolaurate, diglycerol monomyristate, diglycerol monopalmitate, diglycerol monostearate, diglycerol monobehenate, diglycerol monooleate, sorbitan monolaurate Sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monobehenate, sorbitan monolaurate, and the like. These may be used alone or in combination of two or more. In combination it can be used. Particularly preferred are glycerol monostearate, diglycerol monostearate, glycerol monolaurate, diglycerol monolaurate, sorbitan monostearate and those containing at least 20% by mass or more of these.

  Examples of amines and amides include lauryl diethanolamine, myristyl diethanolamine, palmityl diethanolamine, stearyl diethanolamine, oleyl diethanolamine, lauryl diisopropanolamine, myristyl diisopropanolamine, palmityl diisopropanolamine, stearyl diisopropanolamine, oleyl diisopropanolamine, Amine compounds such as N, N-bishydroxyethylalkyl (alkyl group having 12 to 22 carbon atoms) amine, and lauryl diethanolamide, myristyl diethanolamide, palmityl diethanolamide, behenyl diethanolamide, oleyl diethanolamide, lauryl diisopropanolamide , Myristyl diisopropanolamide, Palmityl di-isopropanol amides, stearyl diisopropanolamine amide, there is an amide compound such as oleyl monoisopropanolamide. These can be used alone or in combination of two or more. Preferably, the amine compound is used, and more preferably contains at least 20% by mass of lauryl diethanolamine and stearyl diethanolamine.

Moreover, a known additive can be blended for the purpose of improving the antistatic performance of the above-mentioned compound. Examples thereof include higher alcohols having 12 to 18 carbon atoms, lubricants, silica, calcium silicate and the like. In addition, for the purpose of improving miscibility, a master batch can be used.
The nonionic antistatic agent can be obtained from the market as, for example, Kao Electro Stripper EA, TS-3B, TS-6B, TS-5, TS-2B (trade name), and the like.

  The nonionic antistatic agent is preferably in the range of 0.01 to 10 parts by weight, more preferably 0.1 to 8 parts by weight, and particularly preferably 0.8 to 100 parts by weight of the component (A) of the present invention. It is used in the range of 1 to 5 parts by mass. If the amount used is less than 0.01 parts by mass, the effect of improving antistatic properties cannot be obtained, and if it exceeds 10 parts by mass, the sheet surface appearance tends to be inferior.

  The antistatic resin composition (A) of the present invention and the olefin resin composition (B) of the present invention include known weather resistance (light) agents, antioxidants, heat stabilizers, lubricants, silicone oils, plasticizers. In addition, a sliding agent, a colorant, a dye, a foaming agent, a processing aid (ultra high molecular weight acrylic polymer, ultra high molecular weight styrene polymer), a flame retardant, a crystal nucleating agent, and the like can be appropriately blended.

Moreover, a well-known inorganic or organic filler can be mix | blended with (A) component and (B) component of this 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, mica, kaolin, montmorillonite, hextrite, zinc oxide whisker, titanium There are potassium acid whisker, aluminum borate whisker, plate-like alumina, plate-like silica, and organically treated smectite, aramid fiber, phenol resin, polyester fiber, etc., these are used alone or in combination of two or more. Can be used
Furthermore, for the purpose of improving the dispersibility of the filler, those treated with a known coupling agent, surface treatment agent, sizing agent, etc. can be used. As the known coupling agent, a silane coupling agent can be used. , Titanate coupling agents, aluminum coupling agents, and the like.
The said inorganic or organic filler is normally used in the range of 1-200 mass parts with respect to 100 mass parts of each of the (A) component and (B) component of this invention.

  Further, the component (A) or component (B) of the present invention includes other known polymers such as polyamide resins, polyamide elastomers, polybutylene terephthalate, polyethylene terephthalate, polyarylate, liquid crystal polyester, and other thermoplastic polyester resins, Polyester elastomer, PMMA, methyl methacrylate / maleimide compound copolymer, polyphenylene ether, polyphenylene sulfide, aromatic polycarbonate, thermoplastic polyurethane, ethylene / (meth) acrylate methyl copolymer, ethylene / (meth) acrylic acid copolymer A coalescence, an epoxy resin, a phenol resin, a urea resin, a phenoxy resin, or the like can be appropriately blended.

The multilayer sheet of the present invention comprises at least a layer comprising the component (A) and a layer comprising the component (B). 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 as an extruder during sheeting. The components may be melt-kneaded, and at this time, the components may be used in combination with those previously melt-kneaded.
When melt-kneading in advance, each component can be performed using various extruders, Banbury mixers, kneaders, continuous kneaders, rolls, and the like. In kneading, the respective constituent components may be added together and kneaded, or may be added in portions and kneaded.
The structure of each layer of the multilayer sheet of the present invention is not particularly limited, and for example, it may be foamed or hollow. When foaming the layer composed of the component (B), the foaming agent is not particularly limited, and for example, a known foaming agent used for a foamed polypropylene resin or a foamed polyethylene resin can be used. Specific examples of the blowing agent include inorganic blowing agents such as carbon dioxide, air and nitrogen, volatile blowing agents such as aliphatic hydrocarbons and halogenated hydrocarbons, azodicarbonamide (ADCA), dinitrosopentamethylenetetraamine, Examples include decomposable foaming agents such as azobisisobutyronitrile, hydrazodicarbonamide, and sodium bicarbonate. 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 temperature and the amount of foaming. Moreover, there is no restriction | limiting in particular in the usage-amount of a foaming agent, However, In the case of a decomposition-type foaming agent, it is preferable that it is 0.1-10 mass parts with respect to 100 mass parts of resin compositions for foam molding. When foaming the layer comprising the component (B), the component (A) is 7 to 30% by mass of the olefin resin (A-1) and 5 to 20 mass of the (co) polymer (A-2). %, Polymer (A-3) 15 to 50% by mass, block copolymer (A-4) 20 to 60% by mass of antistatic resin composition (provided that (A-1 ) Component, (A-2) component, (A-3) and (A-4) component is 100% by mass in total).

The multilayer sheet of the present invention is only required to have at least one layer composed of the antistatic resin composition as the component (A) and at least one layer composed of the olefin resin as the component (B). A two-layer sheet comprising a layer composed of the component (A) and a layer composed of the component (B), the layer composed of the component (B) as the core layer, and the layer composed of the component (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. The two-layer sheet and the three-layer sheet are preferable.
The thickness of the multilayer sheet is preferably in the range of 0.2 to 100 mm, 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, particularly preferably 50 μm or more for the purpose of stably developing antistatic properties. It is.

As the method for producing the multilayer sheet, all known methods can be used, and examples thereof include the following methods (1) to (3).
(1) A method in which a sheet of component (A) and a sheet of component (B) are produced and then 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) formed in advance as a sheet or film.
(3) A method of coextruding the component (A) and the component (B) (coextrusion method).
Among these, a particularly preferable method is a coextrusion method.

  In the above, as a method of forming a sheet or film in advance, T-die extrusion molding, inflation molding, calendar molding, and the like are preferable. Moreover, when obtaining by a co-extrusion method, multilayer T-die extrusion molding and multilayer inflation molding are preferable, Especially preferably, it is multilayer T-die extrusion molding, It is preferable to extrude in the range of 160 to 260 degreeC.

The multilayer sheet of the present invention is excellent in antistatic, chemical resistance, impact resistance, and surface appearance, and therefore can be used as a sheet molded product. In addition to the above properties, the multilayer sheet is also excellent in vacuum formability. Therefore, it can be used for various applications by forming a molded article such as a tray by vacuum forming.
The molded product thus obtained includes cases such as a relay case, wafer case, reticle case, mask case, liquid crystal tray, chip tray, hard disk (HDD) tray, CCD tray, IC tray, organic EL tray, optical Used in clean rooms such as pickup-related trays, trays such as LED trays, memory trays, carriers such as IC 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, vending machine internal parts, anti-static bags used for liquid crystal panels, hard disks, plasma panels, plastic cardboard, liquid crystal panels, soft cases for transporting plasma panels, etc. Can be used in the field of materials That.

  EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to such examples as long as the gist of the present invention is not exceeded. In the examples, parts and% are based on mass unless otherwise specified. Various measurements in the examples and comparative examples were based on the following methods.

[1] Evaluation method (1) Gel content of rubbery polymer: According to the above method.
(2) Average particle diameter of rubbery polymer latex;
The average particle diameter 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 Mummant method was used with 70 times integration. In addition, it confirmed with the electron microscope that the particle diameter of the dispersion-grafted rubber-like polymer particle in (A-2) component was substantially the same as the latex particle diameter.
(3) Graft ratio of component (A-2): According to the method described above.
(4) The intrinsic viscosity [η] of the acetone-soluble component of component (A-2);
(5) Component (A-3) (polymer bound styrene content, vinyl bond content, number average molecular weight, and hydrogenation rate);
(5-1) Amount of bound styrene;
It was measured on the polymer before hydrogenation. It was determined from a calibration curve by an infrared method based on absorption of a phenyl group at 699 cm ⁻¹ .
(5-2) Number average molecular weight;
It was measured on the polymer before hydrogenation. It calculated | required from the gel permeation chromatography (GPC).
(5-3) Vinyl bond amount Measured with the polymer before hydrogenation. It calculated | required by the infrared method (Morero method).
(5-4) Hydrogenation rate;
Measurements were taken on the polymer after hydrogenation. Using ethylene tetrachloride as a solvent, was calculated from the spectrum decrease of ¹ H-NMR unsaturated double bond of the spectrum of 100MHz was measured at 15% strength.

(6) Antistatic property;
Using a multi-layer sheet, in accordance with FTMS-101 (US federal test standard), using STATIC DECEY METER 406D manufactured by ETS USA, applying + 5000V under 23 ° C. and humidity 12% RH, then grounding and decaying to 50V Time (seconds) 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 ×: Large crack or break (8) Sheet surface appearance;
The surface of the multilayer sheet was visually evaluated according to the following criteria.
◎: Very good on smooth surface ○: Good appearance on smooth surface ×: Unsmooth surface and poor appearance (9) Using impact-resistant multilayer sheet, in accordance with ASTM-D2794, Dupont impact strength The thickness (kgf · cm) was measured.
(10) Melt flow rate of antistatic resin composition (A) Using sufficiently dried pellets of component (A), melt flow rate (g / g) at 230 ° C. and 2.16 kg load according to JIS K7210: 1999 10 minutes).
(11) Vacuum formability;
Vacuum forming (preheating heater temperature 400 ° C.) was performed using the multilayer sheet to form a tray (dimensions: 400 mm × 500 mm × 50 mm).
O: The target tray molded product was obtained.
X: The sheet hangs down due to preheating and cannot be molded, or the appearance of the molded product was inferior.

[2] Component (1) (A-1) component of antistatic resin composition (A): Polypropylene resin The following polypropylene resin manufactured by Nippon Polypro Co., Ltd. was used as the component (A-1) of the present invention. The melt flow rate was measured at 230 ° C. and a 2.16 kg load in accordance with JIS K7210: 1999.
A1-1; Novatec PP FY6C (trade name)
Homotype, melt flow rate 2.4 g / 10 min A1-2; Novatec PP MA3AH (trade name)
Homotype, melt flow rate 10g / 10min A1-3; Novatec PP EG6D (trade name)
Random type, melt flow rate 1.9 g / 10 min A1-4; Novatec PP MG3ATB (trade name)
Random type, melt flow rate 10g / 10min

(2) (A-2) Component (2-1) Production Example 1; ABS resin In a 7 L glass flask equipped with a stirrer, in a nitrogen stream, 75 parts of ion-exchanged water, 0.5 mg of potassium rosinate Part, tert-dodecyl mercaptan 0.1 part, polybutadiene latex (average particle size: 3500 kg, gel content: 85%) 40 parts (solid content), styrene 15 parts, acrylonitrile 5 parts were added, and the temperature was increased with stirring. . When the internal temperature reached 45 ° C., a solution in which 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.2 parts of glucose were dissolved in 20 parts of ion-exchanged water was added. It was. Thereafter, 0.07 part of cumene hydroperoxide was added to initiate polymerization. After polymerization for 1 hour, 50 parts of ion-exchanged water, 0.7 part of potassium rosinate, 30 parts of styrene, 10 parts of acrylonitrile, 0.05 part of tert-dodecyl mercaptan and 0.01 part of cumene hydroperoxide for 3 hours. Then, the polymerization was continued for another hour, and then 0.2 part of 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol) was added to complete the polymerization. The reaction product latex was coagulated with an aqueous sulfuric acid solution, washed with water, and dried to obtain a rubber-reinforced styrene resin A2-1. The graft ratio of this resin A2-1 was 68%, and the intrinsic viscosity [η] of the acetone-soluble component was 0.45 dl / g.

(2-2) Production Example 2: AS resin Two jacketed polymerization reaction vessels equipped with a ribbon wing with an internal volume of 30 L were connected and purged with nitrogen, and then 75 parts of styrene and 25 parts of acrylonitrile were added to the first reaction vessel. 20 parts of toluene were continuously added. Solution of 0.12 part of tert-dodecyl mercaptan and 5 parts of toluene as molecular weight regulator, and solution of 0.1 part of 1,1′-azobis (cyclohexane-1-carbonitrile) and 5 parts of toluene as polymerization initiator Was fed continuously. The polymerization temperature of the first group was controlled at 110 ° C., the average residence time was 2.0 hours, and the polymerization conversion 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 provided in the second reactor. To the reaction vessel. The polymerization temperature of the second reaction vessel was 130 ° C., and the polymerization conversion was 75%. The copolymer solution obtained in the second reaction vessel was directly devolatilized from the unreacted monomer and solvent using a twin-screw, three-stage vented extruder, and the intrinsic viscosity [η] 0.48 dl / g of styrene resin A2-2 was obtained.

(2-3) Production Example 3; rubber-reinforced styrene resin
(2-3-1) Production of rubber polymer (A2-3a) A stirrer and a jacketed autoclave were dried and purged with nitrogen, and cyclohexane and 20 parts of butadiene solution were charged. Subsequently, n-butyllithium 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 the temperature was increased from 50 ° C to 80 ° C. When the conversion reached 100%, 15 parts of styrene was added, and a polymerization reaction was further performed to obtain an A-B1-B2 triblock copolymer before hydrogenation. The resulting block polymer had 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-vinyl content of 35%. And a polymer having a number average molecular weight of 200,000 consisting of a butadiene block (B2) having a 1,2-vinyl 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 a hydrogenation reaction was performed at 50 ° C. under a hydrogen pressure of 50 kgf / cm ² until the hydrogenation rate was almost 100%, to obtain a rubbery polymer A2-3a. .

(2-3-2) Production of Rubber Reinforced Styrene Resin (A2-3) The above polymer in which a stainless steel autoclave equipped with a ribbon blade was replaced with nitrogen and then made into a uniform solution using toluene as a solvent in a nitrogen stream. A2-3a was charged with 28 parts (solid content), styrene 10.8 parts, acrylonitrile 7.2 parts, methyl methacrylate 54 parts, toluene 120 parts, and tert-dodecyl mercaptan 0.1 part, and the temperature was increased while stirring. . When the internal temperature reaches 50 ° C., 0.5 part of benzoyl peroxide and 0.1 part of dicumyl peroxide are added, and the temperature is further increased. After reaching 80 ° C., the temperature is controlled to be constant at 80 ° C. A polymerization reaction was performed. It took 1 hour from the 6th hour after the start of the reaction, 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, 0.2 part of 2,2-methylenebis-4-6-tert-butylphenol was added, the reaction mixture was extracted from the autoclave, unreacted substances and solvent were distilled off by steam distillation, The polymer was pelletized using a tipped extruder to obtain polymer A2-3. The graft ratio of this product was 45%, and the intrinsic viscosity [η] of the acetone-soluble component was 0.45 dl / g.

(2-4) Production Example 4; rubber reinforced styrene resin
In place of rubber polymer A2-3a, 19 parts of ethylene / propylene rubber (trade name “EP84”, manufactured by JSR) was used, and 57 parts of styrene and 24 parts of acrylonitrile were used instead of styrene / acrylonitrile / methyl methacrylate. Except for the above, a polymerization reaction is carried out in the same manner as in Production Example 3, and a polymer having an ethylene / propylene rubber content of 20%, a graft rate of 55%, and an intrinsic viscosity [η] of 0.45 dl / g of acetone-soluble matter is obtained. A2-4 was obtained.

(3) (A-3) Component (3-1) Production Example 5; Partially Hydrogenated Styrene-Butadiene-Styrene Block Copolymer A cyclohexane solution containing 30 parts of styrene after drying and nitrogen substitution of an agitator and jacketed autoclave Was introduced. 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 and polymerized for 1 hour. Further, a cyclohexane solution containing 30 parts of styrene was added and polymerized for 1 hour. A part of the obtained 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-vinyl 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 at 50 ° C. under a hydrogen pressure of 50 kgf / cm ² for 40 minutes. 0.3 part of 2,6-di-tert-butylcatechol is added to 100 parts of the block copolymer, and then the solvent is removed to obtain a polymer A3-1 having a butadiene portion hydrogenation rate of 69%. It was.

(3-2) Production Example 6: A fully hydrogenated styrene-butadiene block copolymer stirrer and a jacketed autoclave were dried and purged with nitrogen, and a solution of cyclohexane and 20 parts of butadiene was added. Next, 0.025 part of n-butyllithium was added to carry out isothermal polymerization at 50 ° C. When the conversion rate reached 100%, 0.75 parts of tetrahydrofuran and 65 parts of butadiene were added, and the temperature was increased from 50 ° C to 80 ° C. When the conversion reached 100%, 15 parts of styrene was added, and a polymerization reaction was further performed 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-vinyl content 35% butadiene block (B1 block), 1,2-vinyl content 10% butadiene block (B2 block) And a number average molecular weight 200,000 polymer.
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 kgf / cm ² for 2 hours. 2,6-Di-tert-butylcatechol was added in the same manner as in Production Example 5, and then the solvent was removed to obtain a hydrogenated polymer A3-2 having a hydrogenation rate of approximately 100%.

(3-3) Production Example 7: A styrene-butadiene-styrene block copolymer stirrer and a jacketed autoclave were 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 part of n-butyllithium was added, followed by addition of 15.5 parts of styrene and polymerization for 60 minutes (first stage). Next, a mixture of 3 parts of styrene and 20 parts of butadiene was added and polymerized for 60 minutes (second stage). Further, 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, 2,6-di-tert-butylcatechol was added in the same manner as in Production Example 5, the solvent was removed, and the block copolymer A3-3 having three tapered blocks in which polystyrene gradually increased in the polybutadiene block portion. Got. This had a number average molecular weight of 128,000 and a styrene content of 40%.

(3-4) Production Example 8: A styrene-butadiene radial teleblock copolymer stirrer and a 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 a 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 reached 100%. After adding 0.1 part of silicon tetrachloride as a coupling agent, the coupling reaction was completed. After completion of the polymerization, 2,6-di-tert-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.

(4) (A-4) Component The following polymer manufactured by Sanyo Chemical Industries, Ltd. was used as the (A-4) component of the present invention.
A4-1; Pelestat 230 (trade name; polyolefin-polyether block copolymer).
A4-2; Pelestat 303 (trade name; polypropylene-polyether block copolymer).

(5) Other components;
The following were used as other components for improving antistatic properties.
D1; nonionic antistatic agent; electro stripper TS-5 (trade name) glycerin ester D2 manufactured by Kao Corporation; lithium trifluoromethane sulfonate; Sankonol AQ-75T (trade name) lithium trifluoromethane sulfonate manufactured by Sanko Chemical Co., Ltd. 75% aqueous solution D3; zinc oxide whisker; Panatetra WZ-0501 (trade name) manufactured by Matsushita Electric Industrial Co., Ltd.

(5) The following polypropylene manufactured by Nippon Polypro Co., Ltd. was used as the component (B-1). The melt flow rate was measured at 230 ° C. and a 2.16 kg load in accordance with JIS K7210: 1999.
B1-1; Novatec PP EA9BT (trade name)
Homotype, melt flow rate 0.5g / 10min B1-2; Novatec PP EG8 (trade name)
Random type, melt flow rate 0.8g / 10min

(6) The following polyethylene manufactured by Nippon Polyethylene Co., Ltd. was used as the component (B-2). The melt flow rate was measured at 190 ° C. and a 2.16 kg load in accordance with JIS K6922-2.
B2-1; Novatec LD LF122 (trade name)
Low density polyethylene, melt flow rate 0.3g / 10min B2-2; Novatec LD LF280H (trade name)
Low density polyethylene, melt flow rate 0.7g / 10min B2-3; Novatec LD LF440HB (trade name)
Low density polyethylene, melt flow rate 2.8g / 10min

Examples 1-24, Comparative Examples 1-10
(A) A component mixes each structural component by the mixing | blending ratio of Table 1-1 and Table 1-2 with a Henschel mixer, Then, it melt-kneads using a biaxial extruder (cylinder setting temperature 220 degreeC), and a pellet. Turned into. After the obtained pellets were sufficiently dried, the melt flow rate was measured by the above method using the pellets. The results are shown in Table 2.
In Examples 1 to 20 and Comparative Examples 1 to 10, the above component (A) and the component (B) in Table 1-1 and Table 1-2 were used, a three-layer sheet extrusion apparatus was used, and the component (B) was intermediate. A three-layer sheet having both layers as the layers and the component (A) (front and back of the intermediate layer) was 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 each 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 evaluation methods, and the evaluation results are shown in Table 2.
Moreover, 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) in Table 1-1 were used, an azodicarbonamide-based foaming agent was further added to the component (B), and a multilayer T-die extruder was used. Molding was performed at 190 ° C., and a three-layer sheet having a total thickness of 3 mm, in which the foaming ratio of the intermediate layer was 2 and the thickness of both surface layers was 30 μm, was produced.
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.

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. Moreover, the multilayer sheets of Examples 21 to 23 of the present invention are excellent in antistatic properties, chemical resistance, and surface appearance.
Comparative Example 1 is an example in which the blending amount of the olefin resin (A-1) of the antistatic resin composition (A) of the present invention is small outside the scope of the invention, and antistatic properties, chemical resistance, impact resistance , Sheet surface appearance, and vacuum formability are poor. In Comparative Example 2, the blending amount of the component (A-1) is outside the range of the invention, and the blending amounts of the component (A-2), the component (A-3) and the component (A-4) are outside the range of the invention. However, the antistatic property and impact resistance are inferior. 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 the component (A-4) is large outside the scope of the invention, and the impact resistance and sheet surface appearance are inferior. Comparative Example 5 is an example in which the blending amount of the component (A-3) 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 blending amount of the component (A-3) is large outside the scope of the invention, and the impact resistance and the sheet surface appearance are inferior. Comparative Example 7 is an example in which the melt flow rate of the component (B-1) of the olefin resin composition (B) of the present invention was high outside the scope of the invention, but the vacuum moldability was inferior. 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, but the vacuum formability is inferior. In Comparative Example 9, in the blending ratio of the olefin resin composition (B) of the present invention, the amount of the component (B-1) used is outside the scope of the invention, and the amount of the component (B-2) used is that of the invention. There are few examples outside the range, and the vacuum formability is poor. Comparative Example 10 is an example in which the amount of component (B-1) used is small outside the scope of the invention, and the amount of component (B-2) used is large outside the scope of the invention, and the sheet surface appearance and vacuum formability are high. Inferior.

  The multilayer sheet of the present invention has excellent antistatic 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 field, OA / home appliance field, sanitary field, etc.

Claims (8)

A multilayer sheet comprising at least a layer comprising the following component (A) and a layer comprising the following component (B).
(A) component: 7-91 mass% of olefin resin (A-1),
Rubber-reinforced styrene resin obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound in the presence of a rubber polymer, and / or a (co) polymer of the vinyl monomer (A -2) 5-50 mass%,
At least one polymer (A-3) selected from the group consisting of a block copolymer containing a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound and a hydrogenated product thereof ) 2-50 mass%,
2 to 60% by mass of a block copolymer (A-4) containing an olefin polymer block and a hydrophilic polymer block;
Containing an antistatic resin composition (however, the total of the components (A-1), (A-2), (A-3) and (A-4) is 100% by mass).
Component (B): Melt flow, with a melt flow rate (JIS K7210: 1999, measured at 230 ° C. under a load of 2.16 kg) of a polypropylene resin (B-1) having a content of 2.0 g / 10 min. An olefin resin composition comprising 3 to 40% by mass of a polyethylene resin (B-2) having a rate (measured with JIS K6922-2, 190 ° C., 2.16 kg load) of 2.0 g / 10 min or less. The multilayer sheet according to claim 1, wherein the melt flow rate (measured at JIS K7210: 1999, 230 ° C, 2.16 kg load) of the component (A) is 1.0 to 15 g / 10 min. The multilayer sheet according to claim 1 or 2, wherein the olefin resin (A-1) is a random copolymer of propylene and ethylene. The layer comprising the component (B) is a core layer, and the layer comprising the component (A) is a three-layer sheet laminated on both front and back surfaces of the core layer. A multilayer sheet according to claim 1. The multilayer sheet according to any one of claims 1 to 4, wherein the multilayer sheet is obtained by a coextrusion molding method. A molded product obtained by vacuum forming the multilayer sheet according to any one of claims 1 to 5. The multilayer sheet according to any one of claims 1 to 6, wherein the layer made of the component (B) is foamed. The component (A) is 7 to 30% by mass of the olefin resin (A-1), 5 to 20% by mass of the (co) polymer (A-2), and 15 to 50 of the polymer (A-3). Antistatic resin composition comprising 20% by mass and 20-60% by mass of the block copolymer (A-4) (provided that the components (A-1), (A-2), (A- The multilayer sheet according to claim 7, wherein the sum of the components 3) and (A-4) is 100% by mass).