JP2001088251A - Electrification preventing laminated sheet, its production, and molding of sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated sheet which is easy of the molding of an article having a complex shape or a deep drawing shape, especially useful in an application of a tray for electronic devices. and excellent in conductive follow-up properties after being washed with water. SOLUTION: A laminated sheet in which a central base material layer is formed from a high impact polystyrene(HIPS) resin, and each of both surface layers has a resin layer in which a poly(ether ester) or a poly(ether ester amide) is incorporated into the HIPS resin is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a styrene-based resin laminate sheet which has little anti-humidity effect, has excellent antistatic properties with excellent durability, and maintains properties such as adhesion to a substrate and impact resistance. , A manufacturing method thereof, and a molded product.

[0002]

2. Description of the Related Art Styrene-based resin sheets are used for various molded products because of their excellent secondary moldability. Particularly, styrene-based resin sheets are frequently used for trays for transporting electronic devices because of their moldability. I have. However, with the recent development of high-performance and high-sensitivity products in electronic devices, in plastic packaging materials such as trays for these electronic devices, the effects of static electricity generated by friction and the like on electronic devices have increased, and low-voltage discharge has However, there has been a problem that the device is easily destroyed.

[0003] Therefore, in the use of trays for electronic devices, various measures against static electricity have been conventionally studied. For example, a method of mixing a styrene resin sheet with a surfactant has been known. No. 205145 discloses a laminate in which a conductive resin compound layer in which carbon black is kneaded is arranged on the surface of a base sheet made of high impact polystyrene resin (HIPS) or acrylonitrile-butadiene-styrene copolymer resin (ABS resin). The sheet is described.

[0004]

However, a sheet in which a surfactant is kneaded with a thermoplastic resin loses its antistatic effect because the antistatic agent is removed by friction of the surface or washing with water. The content was easily contaminated by the bleed. In particular, in the application of electronic device trays, the film is partially stretched to a high degree because of its fine and fine drawing shape, so that bleeding is liable to occur in the stretched portion, and the stretched portion is subjected to static electricity by friction or water washing. In this case, the conductive bus, which is an escape route, is easily cut off, and the conductive performance is reduced. On the other hand, JP-A-57-20
Although the laminated sheet described in Japanese Patent No. 5145 is excellent in the antistatic effect, it tends to cause carbon black to be detached due to friction, and particularly in the case of trays for electronic devices, causing serious contamination of the devices.

As a technique not using an antistatic agent, for example, Japanese Patent Application Laid-Open No. 9-193316 discloses a technique in which a polyetherester-based antistatic agent is blended into a multilayer acrylic resin sheet. Acrylic resin sheets have excellent rigidity and are used for signboards and lighting covers, but they are inferior in stretchability and cannot be molded into complex shapes or deep drawn products, making it difficult to apply them to trays for electronic devices. Not used for this purpose. Therefore, a sheet that is not molded into such a complicated shape product does not have the problem of bleeding of the antistatic agent in the first place, nor does it have the problem of blocking the conductive path. .

The problem to be solved by the present invention is that molding into a complicated shape or a deep drawing shape typified by the use of an electronic device tray is easy, the interruption of the conductive path can be prevented, and the conductive followability, particularly water washing, can be attained. An antistatic sheet that is excellent in the following conductive follow-up property, and does not further cause contamination of the contents,
An object of the present invention is to provide a method for producing the sheet and a molded product obtained from the sheet.

[0007]

Means for Solving the Problems The inventors of the present invention have developed an antistatic sheet having excellent antistatic ability with excellent durability while maintaining the transparency of the base thermoplastic resin. As a result of intensive studies to develop, it has been found that the above-mentioned problems can be solved by a thermoplastic resin sheet in which a thermoplastic resin layer containing polyetherester or polyetheresteramide as an antistatic agent is laminated on at least one surface. The invention has been completed.

That is, the present invention provides a styrene resin layer (A),
And a styrene-based resin layer (B) containing a polyetherester-based antistatic agent and a styrene-based resin (a).
1) Melt-kneading, and also melt-kneading a polyetherester-based antistatic agent (b1) and a styrene-based resin (b2), and co-extruding the two to form a film. The present invention relates to a method and a molded product obtained by molding the antistatic sheet.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
As described above, the antistatic sheet according to the present invention has a structure in which a styrene resin layer (A) and a styrene resin layer (B) containing a polyetherester antistatic agent are laminated. A characteristic antistatic laminated sheet.

The resin component forming the styrenic resin layer (A) is a styrenic resin (a1). Specifically, GPPS resin, MS resin (methacrylic acid ester-styrene copolymer resin), HIPS Resins containing polystyrene as one of the main components, such as resin (high impact polystyrene resin), MBS resin (methacrylate-butadiene-styrene copolymer resin), and ABS resin (acrylonitrile-butadiene-styrene copolymer resin) Is mentioned.

Among them, from the viewpoints of rigidity and impact strength, rubber-containing HIPS resin, MBS resin or A
BS resin is particularly preferred. These polystyrene resins may be used alone or as a mixture, or a rubber containing styrene as one component, such as a styrene-butadiene block copolymer or a hydrogenated product thereof, may be added. . Further, known resins and rubbers and various additives (lubricants, antioxidants, coloring pigments, inorganic fillers, and the like) may be added as long as the required performance is not impaired. Also, scrap may be collected.

Next, the styrene resin layer (B) is formed with the polyetherester antistatic agent (b1) and the styrene resin (b2) as essential components.

Here, the polyetherester-based antistatic agent (b1) is not particularly limited,
Polyetherester (b1-1) and polyetheresteramide (b1-2) are mentioned.

The polyether ester (b1-1) is not particularly limited, but specific examples include a diol containing a poly (alkylene oxide) glycol unit, an alkylene diol, and a polycarboxylic acid or its alkyl. A polyetherester having a structure having a structure obtained by reacting an ester is exemplified.

The diol containing a poly (alkylene oxide) glycol unit used herein is not particularly limited, but for example, poly (ethylene oxide) glycol, poly (1,2-propylene oxide)
Glycol, poly (1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol,
Poly (hexamethylene oxide) glycol and polyesters, polyamides, polycarbonate compounds containing these, ethylene oxide and propylene oxide block or random copolymers, bisphenol A, bisphenol F, bisphenol S, brominated bisphenol A, 4,4- Bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) amine, and other bisphenols such as polyalkylene oxide) adducts. . These may be used alone or in combination of two or more.

Among these, from the viewpoints of antistatic effect and mechanical properties, the number average molecular weight is 400 to 200,
000 is preferred. That is, by setting the number average molecular weight to 400 or more, the antistatic effect is more significantly improved,
When the number average molecular weight is 200,000 or less,
The mechanical properties of the obtained sheet molded product are good. It is particularly preferable that the number average molecular weight is in the range of 400 to 6,000 from the viewpoint of excellent balance between them.

The diol containing a poly (alkylene oxide) glycol unit is preferably a diol having 2 to 4 carbon atoms as an alkylene oxide structural unit constituting the diol, since the molded article has excellent conductivity. Specific examples of the alkylene oxide structural unit having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, and 1,2.
-Butylene oxide, tetramethylene oxide and the like. The diol may be composed of a single structure of these alkylene oxide structural portions,
Although it may be composed of two or more structural components, it is preferable to contain ethylene oxide as a constituent component particularly from the viewpoint of the antistatic effect of the molded product.

As a material containing such ethylene oxide as a constituent component, poly (ethylene oxide) glycol and bisphenol A ethylene oxide adduct are particularly preferable, since they are particularly excellent in antistatic performance.

In the composition containing ethylene oxide as a component, the content of the ethylene oxide structural site (the ratio of the molecular weight of the ethylene oxide group to the molecular weight of the diol containing a poly (alkylene oxide) glycol unit) is 10% by weight or more. It is preferable from the viewpoint of the antistatic effect.

Further, the diol containing a poly (alkylene oxide) glycol unit is preferably used at a ratio of 40 to 80% by weight based on the ratio of each raw material constituting the polyetherester. That is, when the content is 40% by weight or more, the antistatic effect of the polyetherester becomes good, while when it is 80% by weight or less, the mechanical properties and heat resistance of the obtained polyetherester become good.

The alkylene diol is not particularly limited, but is preferably a diol having 2 to 8 carbon atoms from the viewpoint of antistatic effect and mechanical strength. Specifically, ethylene glycol, propylene glycol,
1,4-butanediol, 1,3-butanediol,
1,2-butylene glycol, trimethylene glycol, neopentyl glycol, diethylene glycol,
2-methyl-1,3-propylene glycol, triethylene glycol, octamethylene glycol, 1,4-
Cyclohexane dimethanol, 1,4-cyclohexanediol and the like can be mentioned. One or more of these may be used.

Among these, the polyetherester obtained has excellent mechanical strength, and therefore has 2 to 4 carbon atoms.
Is preferred, and ethylene glycol is particularly preferred.

Next, examples of the polyvalent carboxylic acid or its alkyl ester include divalent, trivalent and tetravalent or higher polyvalent carboxylic acids or carboxylic anhydrides, and esters of these polyvalent carboxylic acids. May be used alone or as a mixture of two or more.

Specifically, terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,
6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid and their alkyl nucleus-substituted carboxylic acids, halogen nucleus-substituted carboxylic acids, and metal salts of sulfonated phthalic acid Or an aromatic dicarboxylic acid such as a salt thereof;
4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and dicyclohexyl-4,4'-
Alicyclic dicarboxylic acids such as dicarboxylic acids; aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, itaconic acid and dodecane dicarboxylic acid; sulfonated phthalic acid metal salts; Anhydrides and the like.

Examples of the trivalent carboxylic acid include 1,2,4-trimellitic acid, 1,2,5-naphthalenetricarboxylic acid,
2,6,7-naphthalenetricarboxylic acid, 3,3 ′, 4
-Diphenyltricarboxylic acid, benzophenone 3,
3 ′, 4-tricarboxylic acid, diphenyl ether-3,
Aromatic tricarboxylic acids such as 3 ', 4-tricarboxylic acid, substituted alkyl nuclei thereof, and substituted halogen nuclei thereof; aliphatic tricarboxylic acids such as ethylene 1,1,2-tricarboxylic acid and propylene-tricarboxylic acid ;
And their tricarboxylic anhydrides.

Examples of tetravalent carboxylic acids include pyromellitic acid, diphenyl-2,2 ', 3,3'-tetracarboxylic acid, benzophenone-2,2', 3,3'-tetracarboxylic acid and diphenylsulfone-2. , 2 ', 3,3'-tetracarboxylic acid, diphenyl ether-2,2', 3
Aromatic tetracarboxylic acids such as 3′-tetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid and ethylene-1,1,2,2-tetracarboxylic acid, propylene-1,1,3,3 Examples thereof include aliphatic tetracarboxylic acids such as tetracarboxylic acid, and monocarboxylic and tetracarboxylic dianhydrides thereof. One or more of these may be used.

Next, the polycarboxylic acid esters are monoesters, diesters and triesters of the above-mentioned polycarboxylic acids.
It is a compound in which part or all of a polyvalent carboxylic acid such as a tetraester is esterified, and a lower alkyl ester having 6 or less carbon atoms is preferable, and among them, a methyl ester and an ethyl ester are preferable.

Examples of the alkyl ester of such a polycarboxylic acid include, specifically, monomethyl terephthalate, monoethyl terephthalate, dimethyl terephthalate, diethyl terephthalate, dimethyl isophthalate, dimethyl adipate, diethyl malonate and trimethyl phthalate. Monomethyl melitate, monomethyl trimellitic anhydride, trimethyl trimellitate, tetramethyl pyromellitate, tetramethyl ethylenetetracarboxylate, alkyl esters of sulfonated metal phthalates, and the like can be preferably used.

Among these, a divalent carboxylic acid or an alkyl ester thereof is preferable from the viewpoint of polymerizability, color tone of a molded product or mechanical strength physical properties, and particularly, an aromatic ester from the viewpoint of affinity with the styrene resin (b2). Dicarboxylic acids or their alkyl esters are preferred. Further, terephthalic acid, isophthalic acid or an alkyl ester thereof is preferable, and terephthalic acid, dimethyl terephthalate, diethyl terephthalate or dimethyl isophthalate is particularly preferable.

In the present invention, it is preferable to use a metal salt of sulfonated phthalic acid or an alkyl ester thereof as the polycarboxylic acid or an alkyl ester thereof since the antistatic effect is remarkably improved. Therefore, in the present invention, it is preferable to use an aromatic dicarboxylic acid or an alkyl ester thereof as a divalent carboxylic acid and a metal salt of a sulfonated phthalic acid or an alkyl ester thereof as a polyvalent carboxylic acid or an alkyl ester thereof.

The structure of the sulfonated metal phthalate or the alkyl ester thereof used herein is not particularly limited, but the sulfonated metal phthalate or the monoester and diester of the sulfonated metal phthalate are used. Examples thereof include compounds in which part or all of a sulfonated phthalic acid metal salt is esterified, specifically, sodium sulfoterephthalate, potassium sulfoterephthalate, magnesium sulfoterephthalate,
Calcium sulfoterephthalate, sodium sulfoisophthalate, potassium sulfoisophthalate, magnesium sulfoisophthalate, calcium sulfoisophthalate, monomethyl sodium sulfoterephthalate, monomethyl potassium sulfoterephthalate, monomethylmagnesium sulfoterephthalate Monomethyl calcium sulfoterephthalate, dimethyl sodium sulfoterephthalate, dimethyl potassium sulfoterephthalate, dimethylmagnesium sulfoterephthalate,
Sulfoterephthalic acid dimethyl calcium salt, sulfoisophthalic acid monomethyl sodium salt, sulfoisophthalic acid monomethyl potassium salt, sulfoisophthalic acid monomethyl magnesium salt, sulfoisophthalic acid monomethyl calcium salt, sulfoisophthalic acid dimethyl sodium salt, sulfoisophthalic acid dimethyl potassium salt, sulfo Examples include dimethylmagnesium isophthalate and dimethylcalcium sulfoisophthalate.

As the ester form of the sulfonated phthalic acid metal salt, a lower alkyl ester having 6 or less carbon atoms such as a methyl ester or an ethyl ester is preferably used. One or more of these are used.

In the present invention, when a trivalent or higher polycarboxylic acid such as trimellitic acid or pyromellitic acid is used in addition to these dicarboxylic acids, the molecular weight of the target polyether ester can be easily increased. It is preferable because it can be raised.

The production of the polyetherester used in the present invention from the above-mentioned components is not particularly limited. For example, method 1: poly (alkylene oxide) glycol, alkylene glycol and polycarboxylic acid Or a method of obtaining a polyetherester having a terminal hydroxyl group by reaction with an ester thereof, and then, if necessary, reacting the polyetherester with a sulfonated metal phthalate or an ester thereof to obtain a target polyetherester;

Method 2: Reaction of poly (alkylene oxide) glycol, alkylene glycol and, if necessary, sulfonated metal phthalate or an ester thereof, to obtain a polyetherester having a terminal hydroxyl group. A method of adding a glycol and / or an alkylene glycol, and then reacting with a polycarboxylic acid or an ester thereof to obtain an intended polyether ester;

Method 3: Polyetherester is obtained by reacting a poly (alkylene oxide) glycol, an alkylene glycol, and if necessary, a sulfonated metal salt of phthalic acid or an ester thereof, and a polycarboxylic acid or an ester thereof. Method and the like.

In each of the above methods 1 to 3, when the poly (alkylene oxide) glycol, the alkylene glycol, and the polycarboxylic acid or its ester are reacted, specifically, at 100 to 200 ° C. under normal pressure. The reaction can be carried out at a temperature of 200 to 300 ° C., and the reaction can be carried out under reduced pressure.

The molecular weight and the like of the polyetherester (b1-1) thus obtained are not particularly limited, but specifically, the number average molecular weight measured by GPC is 10,000 to 500. 2,000 is preferred.

In the present invention, all the number average molecular weights measured by GPC are GPC (Tosoh Build-up GP)
C) using [mobile phase: 5 mmol / L CF3C00
Na / HFIP, column thermostat: 40 ° C, detector: UV
(220 nm), column: Shodex GPC HF
IP-805 + HFIP-806].

In the present invention, as described above, it is preferable to use a sulfonated metal salt of phthalic acid or an ester thereof in view of further improving the antistatic effect. The amount of the sulfonic acid metal base contained in b1-1) is preferably in a range of 0.1 to 2% by weight as a measured value of the amount of metal ions by inductively coupled plasma emission spectrometry after pretreatment with acid decomposition. .

Further, polyetherester (b1-1)
In the case of using an aromatic dicarboxylic acid or an ester thereof, the ratio of the hard segment in the amount of the structural site caused by the aromatic dicarboxylic acid or the ester thereof is as follows:
Although not particularly limited, the aromatic dicarboxylic acid or the aromatic dicarboxylic acid occupied in each raw material constituting the polyetherester (b1-1) is preferable in that the balance between the antistatic effect and the impact resistance of the molded product is improved. 5 to 5% of the ester
It is preferably used in the range of 70% by weight. That is,
When the content is 5% by weight or more, the mechanical properties of the molded product become good, and when it is 70% by weight or less, the antistatic effect of the molded product becomes remarkably good. In particular, the content is preferably in the range of 10 to 50% by weight from the viewpoint of excellent balance between them.

Next, the polyetherester amide (b1-2) used as the polyetherester-based antistatic agent (b1) in the present invention includes aminocarboxylic acid or lactam, polyvalent carboxylic acid or an alkyl ester thereof,
A diol containing a poly (alkylene oxide) glycol unit, and a polyetheresteramide (b1-2-) having a structure obtained by reacting an alkylenediol
a) and a polyether ester amide (b1-2-b) having a structure obtained by reacting a diol containing a poly (alkylene oxide) glycol unit, an alkylene diol, a polyvalent carboxylic acid or an alkyl ester thereof, and a diamine compound. ) And the like.

Here, polyetheresteramide (b)
The aminocarboxylic acid or lactam used in 1-2-a) is not particularly limited. Examples of the aminocarboxylic acid include ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, and ω-aminopergon. Acid, ω
-Aminocapric acid, 11-aminoundecanoic acid, 12
Aminocarboxylic acids such as aminodecanoic acid; and lactams such as caprolactam, enantholactam, laurolactam, undecanolactam and the like.

Next, polyetheresteramide (b1-
Examples of the diamine compound used in 2-b) include, but are not particularly limited to, aromatic diamines, alicyclic diamines, and aliphatic diamines. Of these, hexamethylene diamine is preferred. And aliphatic diamines such as heptamethylenediamine, octamethylenediamine and decamethylenediamine, with hexamethylenediamine being particularly preferred.

Next, polyetheresteramide (b1
-2-a) and polyetheresteramide (b1-2)
Any of the above-mentioned diols and alkylene diols containing a poly (alkylene oxide) glycol unit used in -b) can be used. Specifically, as the diol containing a poly (alkylene oxide) glycol unit used here, Is not particularly limited, for example, poly (ethylene oxide) glycol, poly (1,
2-propylene oxide) glycol, poly (1,3-
Propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol and polyesters, polyamides, polycarbonate compounds containing these, block or random copolymers of ethylene oxide and propylene oxide, bisphenol A, bisphenol F , Bisphenol S, brominated bisphenol A, 4,4-bis (4-
(Hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl)
Ether, bis (4-hydroxyphenyl) amine and other bisphenols, and polyalkylene oxide) adducts. These may be used alone or in combination of two or more.

Among these, from the viewpoints of antistatic effect and mechanical properties, the number average molecular weight is 400 to 200,
000 is preferred. That is, by setting the number average molecular weight to 400 or more, the antistatic effect is more significantly improved,
When the number average molecular weight is 200,000 or less,
The mechanical properties of the obtained sheet molded product are good. It is particularly preferable that the number average molecular weight is in the range of 400 to 6,000 from the viewpoint of excellent balance between them.

The diol containing a poly (alkylene oxide) glycol unit is preferably a diol having 2 to 4 carbon atoms as an alkylene oxide structural unit constituting the diol, since the molded article has excellent conductivity. Specific examples of the alkylene oxide structural unit having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, and 1,2.
-Butylene oxide, tetramethylene oxide and the like. The diol may be composed of a single structure of these alkylene oxide structural portions,
Although it may be composed of two or more structural components, it is preferable to contain ethylene oxide as a constituent component particularly from the viewpoint of the antistatic effect of the molded product.

As a material containing such an ethylene oxide as a constituent component, poly (ethylene oxide) glycol and bisphenol A ethylene oxide adduct are particularly preferable, since they are particularly excellent in antistatic performance.

In the case of the composition containing ethylene oxide, the content of the ethylene oxide structural site (the ratio of the molecular weight of the ethylene oxide group to the molecular weight of the diol containing the poly (alkylene oxide) glycol unit) is 10% by weight or more. It is preferable from the viewpoint of the antistatic effect.

Further, the diol containing a poly (alkylene oxide) glycol unit is preferably used in a ratio of 40 to 80% by weight of each raw material constituting the polyetherester. That is, when the content is 40% by weight or more, the antistatic effect of the polyetherester becomes good, while when it is 80% by weight or less, the mechanical properties and heat resistance of the obtained polyetherester become good.

Next, a polyetheresteramide (b1
-2-a) and polyetheresteramide (b1-2)
The alkylene diol used in -b) is not particularly limited, but is preferably a diol having 2 to 8 carbon atoms from the viewpoint of antistatic effect and mechanical strength. Specifically, ethylene glycol, propylene glycol 1,4-butanediol, 1,3-butanediol, 1,2-butylene glycol, trimethylene glycol, neopentyl glycol, diethylene glycol, 2-methyl-1,3-propylene glycol, triethylene glycol, octamethylene glycol , 1,
4-cyclohexanedimethanol, 1,4-cyclohexanediol and the like can be mentioned. One or more of these may be used.

Among these, the obtained polyether ester (b1-2-a) and polyether ester (b1
Alkylene diols having 2 to 4 carbon atoms are preferred because of the excellent effect of improving the mechanical strength of -b), and ethylene glycol is particularly preferred.

Next, polyetheresteramide (b1
-2-a) and polyetheresteramide (b1-2)
As the polyvalent carboxylic acid or its alkyl ester used in -b), any of those exemplified in (b1-1) can be used. For example, divalent, trivalent and tetravalent or higher polyvalent carboxylic acids or carboxylic acids can be used. Examples thereof include anhydrides and esters of these polycarboxylic acids, which may be used alone or as a mixture of two or more.

Specifically, terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,
6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid and their alkyl nucleus-substituted carboxylic acids, halogen nucleus-substituted carboxylic acids, and metal salts of sulfonated phthalic acid Or an aromatic dicarboxylic acid such as a salt thereof;
4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and dicyclohexyl-4,4'-
Alicyclic dicarboxylic acids such as dicarboxylic acids; aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, itaconic acid and dodecane dicarboxylic acid; sulfonated phthalic acid metal salts; Anhydrides and the like.

Examples of the trivalent carboxylic acid include 1,2,4-trimellitic acid, 1,2,5-naphthalenetricarboxylic acid,
2,6,7-naphthalenetricarboxylic acid, 3,3 ′, 4
-Diphenyltricarboxylic acid, benzophenone 3,
3 ′, 4-tricarboxylic acid, diphenyl ether-3,
Aromatic tricarboxylic acids such as 3 ', 4-tricarboxylic acid, substituted alkyl nuclei thereof, and substituted halogen nuclei thereof; aliphatic tricarboxylic acids such as ethylene 1,1,2-tricarboxylic acid and propylene-tricarboxylic acid ;
And their tricarboxylic anhydrides.

Examples of tetravalent carboxylic acids include pyromellitic acid, diphenyl-2,2 ', 3,3'-tetracarboxylic acid, benzophenone-2,2', 3,3'-tetracarboxylic acid, and diphenylsulfone-2. , 2 ', 3,3'-tetracarboxylic acid, diphenyl ether-2,2', 3
Aromatic tetracarboxylic acids such as 3′-tetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid and ethylene-1,1,2,2-tetracarboxylic acid, propylene-1,1,3,3 Examples thereof include aliphatic tetracarboxylic acids such as tetracarboxylic acid, and monocarboxylic and tetracarboxylic dianhydrides thereof. One or more of these may be used.

Next, polyvalent carboxylic acid esters include the monoesters, diesters and triesters of the polyvalent carboxylic acids.
It is a compound in which part or all of a polyvalent carboxylic acid such as a tetraester is esterified, and a lower alkyl ester having 6 or less carbon atoms is preferable, and among them, a methyl ester and an ethyl ester are preferable.

Examples of such alkyl esters of polycarboxylic acids include, specifically, monomethyl terephthalate, monoethyl terephthalate, dimethyl terephthalate, diethyl terephthalate, dimethyl isophthalate, dimethyl adipate, diethyl malonate, and trimethyl phthalate. Monomethyl melitate, monomethyl trimellitic anhydride, trimethyl trimellitate, tetramethyl pyromellitate, tetramethyl ethylenetetracarboxylate, alkyl esters of sulfonated metal phthalates, and the like can be preferably used.

Among these, a divalent carboxylic acid or an alkyl ester thereof is preferable from the viewpoints of polymerizability, color tone of a molded product, and mechanical strength physical properties, and particularly, an aromatic dicarboxylic acid or an aromatic dicarboxylic acid from the viewpoint of affinity with a styrene resin. The alkyl ester is preferred. Further, terephthalic acid, isophthalic acid or an alkyl ester thereof is preferable, and terephthalic acid, dimethyl terephthalate, diethyl terephthalate or dimethyl isophthalate is particularly preferable.

In the present invention, the use of a metal salt of sulfonated phthalic acid or an alkyl ester thereof as the polyvalent carboxylic acid or an alkyl ester thereof is preferred because the antistatic effect is dramatically improved. Therefore,
In the present invention, it is preferable to use an aromatic dicarboxylic acid or an alkyl ester thereof as a divalent carboxylic acid and a metal salt of a sulfonated phthalic acid or an alkyl ester thereof as a polyvalent carboxylic acid or an alkyl ester thereof.

The structure of the sulfonated phthalic acid metal salt or its alkyl ester used herein is not particularly limited, but the sulfonated phthalic acid metal salt or the monoester and diester of the sulfonated phthalic acid metal salt are used. Examples thereof include compounds in which part or all of a sulfonated phthalic acid metal salt is esterified, specifically, sodium sulfoterephthalate, potassium sulfoterephthalate, magnesium sulfoterephthalate,
Calcium sulfoterephthalate, sodium sulfoisophthalate, potassium sulfoisophthalate, magnesium sulfoisophthalate, calcium sulfoisophthalate, monomethyl sodium sulfoterephthalate, monomethyl potassium sulfoterephthalate, monomethylmagnesium sulfoterephthalate Monomethyl calcium sulfoterephthalate, dimethyl sodium sulfoterephthalate, dimethyl potassium sulfoterephthalate, dimethylmagnesium sulfoterephthalate,
Sulfoterephthalic acid dimethyl calcium salt, sulfoisophthalic acid monomethyl sodium salt, sulfoisophthalic acid monomethyl potassium salt, sulfoisophthalic acid monomethyl magnesium salt, sulfoisophthalic acid monomethyl calcium salt, sulfoisophthalic acid dimethyl sodium salt, sulfoisophthalic acid dimethyl potassium salt, sulfo Examples include dimethylmagnesium isophthalate and dimethylcalcium sulfoisophthalate.

As the ester of the sulfonated phthalic acid metal salt, a lower alkyl ester having 6 or less carbon atoms such as methyl ester or ethyl ester is preferably used. One or more of these are used.

In the present invention, when a trivalent or higher polycarboxylic acid such as trimellitic acid or pyromellitic acid is used in addition to these dicarboxylic acids, the molecular weight of the target polyether ester can be easily reduced. It is preferable because it can be raised.

The production of the polyetheresteramide (b1-2) used in the present invention from each of the above-mentioned components is not particularly limited. For example, Method 3: Reaction of aminocarboxylic acid or lactam with dicarboxylic acid To form a polyamide having a terminal carboxyl group, and reacting the polyamide with a diol containing a poly (alkylene oxide) glycol unit and an alkylene diol. Method 4: An aminocarboxylic acid or lactam, a dicarboxylic acid and a poly (alkylene oxide) glycol unit. Method of reacting diol containing alkylene diol with alkylene diol, method 5: producing a salt of diamine compound and dicarboxylic acid, and reacting diol containing poly (alkylene oxide) glycol unit with alkylene diol. .

The molecular weight and the like of the polyetheresteramide (b1-2) thus obtained are not particularly limited, but specifically, the number average molecular weight measured by GPC is from 10,000 to Those in the range of 500,000 are preferred.

Further, from the viewpoint that the balance between the antistatic effect and the impact resistance of the molded article is improved, the ratio of the aromatic dicarboxylic acid or its ester to the raw materials constituting the polyetheresteramide (b1-2) is considered. Is preferably used in the range of 5 to 70% by weight. That is, when the content is 5% by weight or more, the mechanical properties of the molded product become good. When the content is 70% by weight or less, the antistatic effect of the molded product becomes extremely good. In particular, the content is preferably in the range of 10 to 50% by weight from the viewpoint of excellent balance between them.

Next, as the styrene resin (b2) constituting the styrene resin layer (B), specifically, GPP
S resin, MS resin (methacrylic ester-styrene copolymer resin), HIPS resin (high impact polystyrene resin), MBS resin (methacrylic ester-butadiene-styrene copolymer resin), ABS resin (acrylonitrile-butadiene-styrene) And polystyrene as one of the main components, such as a copolymer resin).

Among these, rubber-containing HIPS resin, MBS resin or ABS resin is particularly preferable in terms of rigidity and impact resistance. These polystyrene resins may be used alone or as a mixture, or a rubber containing styrene as one component, such as a styrene-butadiene block copolymer or a hydrogenated product thereof, may be added. . Further, known resins and rubbers and various additives (lubricants, antioxidants, coloring pigments, inorganic fillers, and the like) may be added as long as the required performance is not impaired. Also, scrap may be collected.

The mixing ratio of the above-mentioned polyetherester-based antistatic agent (b1) and styrene-based resin (b2) as the resin component forming the styrene-based resin layer (B) is not particularly limited. The blending ratio of the polyetherester-based antistatic agent (b1) is 2 to 40% by weight.
Is preferable from the viewpoints of the antistatic effect and the impact resistance.

The styrene resin layer (B) includes
Not only the above-mentioned polyetherester-based antistatic agent (b1) and styrene-based resin (b2), but also a copolymer of a styrene-based monomer and an acid group-containing vinyl-based compound (b3)
Is preferred from the viewpoint of increasing the dispersibility of the polyetherester-based antistatic agent (b1) in the layer (B).

Here, the blending ratio of the copolymer (b3) of the styrene monomer and the acid group-containing vinyl compound is not particularly limited, but the mixing ratio of the polyetherester antistatic agent (b1) is not limited. The content is preferably 1 to 30% by weight from the viewpoint of excellent dispersibility improving effect and further improving antistatic effect.

The styrenic monomer constituting the copolymer (b3) is not particularly limited, but styrene and α-
Methylstyrene and the like can be mentioned.

On the other hand, examples of the acid group-containing vinyl compound constituting the copolymer (b3) include, but are not particularly limited to, vinyl compounds having a carboxyl group or an acid anhydride group. Group-containing vinyl monomers are preferred.

The carboxyl group-containing vinyl monomer includes, for example, (meth) acrylic acid, crotonic acid,
Vinyl-based monomers having a carboxyl group such as cinnamic acid, itaconic acid and maleic acid can be mentioned. Among these, (meth) acrylic acid is particularly preferred because of its good reactivity with styrene monomers.

In the present invention, the copolymer (b3)
May be obtained by copolymerizing other vinyl monomers in addition to the styrene monomer and the acid group-containing vinyl compound as required.

Here, the other vinyl monomer is not particularly limited as long as it is a monomer having a vinyl group. For example, ethylene, chlorinated ethylene, vinylidene chloride, propylene, methylpentene, acrylonitrile,
Examples include acrylates such as vinyl acetate, 1-butene, and methyl acrylate, and methacrylates such as methyl methacrylate.

The method for producing the copolymer (b3) of a styrene monomer and an acid group-containing vinyl compound is not particularly limited. And copolymerization in the presence of an initiator.

The molecular weight of the copolymer (b3) is not particularly limited. For example, the weight average molecular weight is 2,000.
It is preferably in the range of ~ 500,000. When the weight average molecular weight is 2,000 or more, the impact resistance of the molded article is improved, and when it is 500,000 or less, the appearance of the molded article after compounding is excellent. Particularly preferably, the weight average molecular weight is in the range of 10,000 to 400,000.

The amount of the acid group contained in the copolymer (b3) is not particularly limited, but is preferably in the range of 0.001 to 7.5 mgKOH / g in terms of the effect of compatibilization. That is, the effect of improving the dispersibility becomes remarkable at 0.001 mgKOH / g or more, and the impact strength of the molded article is remarkably improved, while the appearance of the molded article obtained at 7.5 mgKOH / g or less is excellent. It will be. Among these points, the performance balance is particularly excellent, and the acid value is 0.001 to 0.001.
A range of 1.5 mg KOH / g is preferred.

The styrene resin layer (B) may further contain a known antistatic agent such as an ionic antistatic agent, depending on the use. As these known ionic antistatic agents, for example,

[0081]

Formula 1 A sulfonic acid metal salt represented by R-SO3M is exemplified.

The metal sulfonic acid salt represented by 1 may be any metal metal sulfonic acid salt in which R is an alkyl group or an alkylaryl or aryl group and M is an alkali metal or an alkaline earth metal. Is, particularly, R is an alkyl group or alkylaryl group having about 8 to 30 carbon atoms, M is Na, K, Li, Mg,
Those selected from Ca and the like are preferable.

Specific examples of such sulfonic acid metal salts include sodium octyl sulfonate, sodium nonyl sulfonate, sodium decyl sulfonate, sodium dodecyl sulfonate, sodium octadecyl sulfonate, sodium decyl benzene sulfonate, and dodecyl benzene sulfonate. Sodium, sodium stearylbenzenesulfonate, sodium octylbenzenesulfonate, sodium octylnaphthalenesulfonate, sodium dodecylnaphthalenesulfonate, potassium dodecylsulfonate, lithium dodecylsulfonate, lithium dodecylbenzenesulfonate, magnesium dodecylsulfonate, dodecylsulfonate Calcium and the like can be mentioned.

Among them, sodium dodecylbenzenesulfonate and sodium dodecylsulfonate are preferably used.

The metal salt of sulfonic acid represented by the formula 1 is not always necessary, but is added to the antistatic resin composition of the present invention in a small amount, so that the metal salt of sulfonic acid interacts with polyetherester and polyetheresteramide. This is preferable because the antistatic performance is significantly improved. Specifically, the addition amount is 5% by weight or less in the layer (B) to improve the antistatic performance without roughening the surface of the molded product, coloring, or deteriorating physical properties. It is preferable because it can be performed. Especially, the range of 0.1 to 3% by weight is most preferable.

The layers (A) and (B) of the present invention may be used, if necessary, in a range not impairing the effects of the present invention, such as general-purpose resins such as olefin resins and polyester resins, polycarbonates, PPE resins, and PPS resins. And other thermoplastic resins.

The styrene resin (a1) constituting the styrene resin layer (A) and the styrene resin layer (B)
It is preferable to use the same or similar resin as the styrene-based resin (b2) constituting from the viewpoint that the adhesion between the layer (A) and the layer (B) is improved.

Here, as the same resin, preferable combinations are as follows: (a1) and (b2) are both HIPS resins; (a1) and (b2) are both MBS resins; (B2) is a case where both are ABS resins, and in particular, (a) in terms of rigidity and impact resistance.
It is preferable that both 1) and (b2) are HIPS resins, and that both (a1) and (b2) are MBS resins.

Preferred examples of the case of using the same type of resin are as follows: (a1) is an MBS resin, (b2) is a HIPS resin and M
(A1) is an ABS resin and (b2) is a HIPS resin and A
(A1) is an MBS resin and (b2) is a HIPS resin, (a1) is an ABS resin and (b2) is a HIPS resin, (a1) is a HIPS resin The case where (b2) is an MBS resin or the like is mentioned, but it is easy to adjust the raw material compound at the time of subjecting it to extrusion film forming, and the obtained sheet is excellent in rigidity and impact resistance. Combinations are preferred.

Further, a resin for improving the affinity is added to either the styrene-based resin (a1) or the styrene-based resin (b2), or both the styrene-based resin (a1) and the styrene-based resin (b2) are provided between the (A) layer and the (B) layer. An adhesive layer having an affinity may be interposed in the layer.

The components constituting the styrenic resin layer (B) may be introduced into an extruder during sheet production and subjected to melt-kneading, but the polyetherester-based antistatic agent (b1) may be used in advance. A styrene resin (b2), and, if necessary, a copolymer of a styrene monomer and an acid group-containing vinyl compound (b3), and various other components described above, are subjected to Banbury mixer, co-kneader, single screw or twin screw extrusion. It is preferred that the compound is produced in advance by kneading with a kneader or the like. When used, the compound may be used alone, or the compound may be diluted with a styrene resin (b2) before use.

The styrene resin layer (A) described in detail above,
The antistatic sheet of the present invention comprising a styrene-based resin layer (B) containing a polyetherester-based antistatic agent (b1) and a polyetherester-based antistatic agent (b1) has, as its layer structure, a layer (A) and a layer (B) on at least one surface. Styrene-based resin layers (B) on both sides of the styrene-based resin layer (A) in order to further improve the conductive follow-up property and to prevent a difference in performance between the front and back of the antistatic sheet. ) Are stacked, and the layer structure is preferably (B) / (A) / (B).

Further, a further multi-layer structure, for example,
The structure such as (B) / (A) / (B) / (A) / (B) may be used, or the (A) layer and (B)
An intermediate layer may be provided between the layers to improve adhesion.

The ratio of the thickness of the styrene resin layer (A) to the thickness of the styrene resin layer (B) is not particularly limited, but the sum of the (B) layers / the sum of the (A) layers = 50/50 to 1 / 9
A range of 9 is preferable, but a range in which the thickness of one styrene resin layer (B) is 3 to 25% of the thickness of the entire sheet is particularly preferable from the viewpoint of sheet strength and the like. Also, in order not to cause a difference in performance between the front and back of the antistatic sheet,
It is preferable that the layers that come to the outermost layer on both sides as the (B) layer have the same thickness.

The specific thickness is not particularly limited because it can be appropriately set depending on the application, but the total of the styrene resin layer (A) with respect to the entire laminated sheet is 0.0%.
The total of the styrene resin layer (B) containing 9 to 1.9 mm and 2 to 40% by weight of the antistatic agent is 0.01 to 0.4 mm, and the (A) layer and the (B) layer Vacuum forming, the total thickness of the laminated state is 0.1 to 2.0 mm,
It is preferable because it is suitable for molding methods such as pressure forming and press molding.

The method for producing the antistatic sheet of the present invention described in detail above is not particularly limited.
For example, a method of manufacturing a laminated sheet by a known laminating method such as a method in which one of the sheets corresponding to the layers (A) and (B) is formed in advance and extruded and laminated on the other may be used. (A1) is melt-kneaded, the polyetherester antistatic agent (b1) and the styrene resin (b2) are melt-kneaded, and both are co-extruded to form a film. Is preferable because it dramatically improves.

As the latter method, specifically, a styrene-based resin (a1) and, if necessary, other compounding components are charged into an extruder and melt-kneaded, while a polyetherester-based antistatic agent (b1), a styrene-based Resin (b2), and further, if necessary, a copolymer (b3) of a styrene monomer and an acid group-containing vinyl compound, and other various components, or a compound thereof, or a styrene resin ( A method in which the mixture diluted in b2) is charged into another extruder, melt-kneaded, and then a laminated sheet is formed by coextrusion using a T-die.

The laminating method is not particularly limited, but a laminated sheet can be obtained by a generally known feed block method, multi-die method or the like. The lip opening of the T-die is preferably set to be equal to or slightly wider than the target sheet thickness.

The film forming temperature varies depending on the type of the resin used.
It is preferable that it is in the range of -230 ° C.

The thickness of the obtained laminated sheet is 0.1 to 2.0 mm as described above, since it is suitable for forming methods such as vacuum forming, pressure forming and press forming.
Is preferred.

The above-mentioned antistatic sheet can be formed into a molded article of the present invention by a usual molding method. More specifically, the heat-softened sheet is vacuum-molded in close contact with the mold by vacuum, press-molded in close contact with the mold by pressurized air, compressed-air vacuum forming using both vacuum and pressurized, and male and female molds. Press molding and the like. The molding method is not limited to this.

As described above, the present invention has a feature that the antistatic performance is not deteriorated even when forming into a complicated shape or a deep drawing shape. It is preferable that the product has a draw ratio of 0.8 to 1.5 because the effect of the present invention is remarkable.

The molded article of the present invention has an excellent antistatic property even in the stretched portion and has a long lasting antistatic effect, so that it is useful as various packaging materials. Useful in parts packaging applications.

[0104]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Each characteristic value in the examples was evaluated according to the following methods.

1. Surface resistivity The laminated sheet obtained in each Example or Comparative Example was heated at 23 ° C.
A sheet sample (100 × 100 mm) was prepared by adjusting the condition at a relative humidity of 50% for 24 hours.
In accordance with K-6911, Advantest digital ultra-high resistance meter R8340 and resistivity chamber R
The measurement was performed using 12702 under the conditions of an applied voltage of 10 V, an applied time of 1 minute, and a measurement time of 1 minute. Next, the sheet sample was washed with running water (20 ° C.) for 30 minutes, and was washed at 23 ° C. and a relative humidity of 50 ° C.
After conditioning for 24 hours, the surface resistivity was measured under the same conditions as before washing. The surface resistance of the sheet was determined according to the following criteria. Surface resistance value criterion ◎: Surface resistance value less than 10 ¹¹ Ω ○: Surface resistance value of 10 ¹¹ Ω or more and less than 10 ¹³ Ω ×: Surface resistance value of 10 ¹³ Ω or more

2. Conductive Followability (= Surface Resistivity after Sheet Stretching) The laminated sheet obtained in each Example or Comparative Example was subjected to a research polymer film biaxial stretching apparatus BIX-70 manufactured by Iwamoto Seisakusho
Using 2S, tank temperature 120 ° C, stretching speed 10mm /
The sheet sample was simultaneously biaxially stretched at a stretching surface magnification of 5.0 times (corresponding to a drawing ratio of 1) for 30 minutes, and then the sheet sample was washed with running water (20 ° C.) for 30 minutes, and at 23 ° C. and a relative humidity of 50% for 24 hours. After the state adjustment, the surface resistivity after stretching was determined according to the following criteria. Criteria for determining conductivity followability ◎: Surface resistivity less than 10 ¹¹ Ω ○: Surface resistivity 10 ¹¹ Ω or more and less than 10 ¹³ Ω ×: Surface resistivity 10 ¹³ Ω or more

3. Tensile modulus According to JIS K-7127, the tensile modulus was measured using an autograph manufactured by Shimadzu Corporation. The tensile modulus of the sheet was determined according to the following criteria. Criteria for judging tensile modulus ◎: Tensile modulus 1.8 GPa or more 以上: Tensile modulus 1.5 GPa or more and less than 1.8 GPa: Tensile modulus 1.2 GPa or more and less than 1.5 GPa ×: Tensile modulus 1.2 GPa Less than

4. Evaluation method of bleed-out property The obtained sheet was cut into a 10 cm × 10 cm sample and placed in a gear oven set at 80 ° C. for 48 hours. Thereafter, a transparent pressure-sensitive adhesive tape was stuck on the sheet surface and peeled off, and then the presence or absence of an adhered substance on the pressure-sensitive adhesive tape was observed and evaluated. ：: No deposits. X: There is a deposit.

5. Transparent polymer biaxial stretching machine BI for research
Using X-702S, tank temperature 120 ° C, stretching speed 10
mm / sec, simultaneous biaxial stretching at a stretching surface magnification of 5.0 times,
The stretched sheet was placed on newsprint, and the transparency was visually determined. ○ indicates that the characters on the newspaper were discriminated, and X indicates that the discrimination was not possible.

6. Peelability A drop weight impact test using a DuPont impact tester was performed, and the penetration was determined by visually observing the penetrating surface after pulling out the load. ○
Indicates that no surface peeling occurred, and x indicates that surface peeling occurred.

7. Layer Configuration The layer configuration of the base sheet was measured using an epi-illumination microscope.

8. According to MFR JIS K-7210, temperature 200 ° C, load 5k
gf.

Resins used in the following Examples and Comparative Examples were
It is as follows. [Resins used as styrene resins (a1) and (b2)] A resin (Mw = 210,000, rubber amount = 8% by weight, MFR = 3) is used as HIPS (high impact polystyrene). Hereinafter, this is abbreviated as resin R-1. 2. Use "Clearpact TI350" manufactured by Dainippon Ink and Chemicals as MBS resin. Hereinafter, this is abbreviated as Resin R-2.

[Resin used as dispersant (b3)] A styrene / methacrylic acid (90/10 (weight ratio)) copolymer was used as a copolymer of a styrene monomer and an acid group-containing vinyl compound. This is abbreviated as C-1.

[Polyetherester antistatic agent (b
Resin used as 1)] In a flask equipped with a temperature controller, a stirring blade and a nitrogen inlet tube, 600 parts of poly (ethylene oxide) glycol having a number average molecular weight of 2040, 394 parts of dimethyl terephthalate, 29 parts of dimethyl sodium sulfoisophthalate 29 parts 396 parts of ethylene glycol and 2.8 parts of calcium acetate as a catalyst were charged, and stirring was continued while removing methanol over 2 hours at 180 ° C. under a flow of nitrogen. Then, the reaction was allowed to proceed at 210 ° C. for 2 hours while removing an extract such as excess ethylene glycol under a reduced pressure of 5 mmHg. Further, 1.5 parts of tetrabutyl titanate was added as a catalyst, and the temperature was raised to 250 ° C. Then, after reacting under a reduced pressure of 0.3 mmHg for 3 hours, the reaction mixture was taken out in a strand form under nitrogen pressure, and pelletized to obtain a polyetherester. This polyetherester is used as an antistatic agent, and is hereinafter abbreviated as antistatic agent S-1. "Pelestat 6321" manufactured by Sanyo Chemical Industries, Ltd. is used as the polyetheresteramide, and is hereinafter abbreviated as antistatic agent S-2.

[Production of antistatic agent-containing resin component] The antistatic agent-containing resin component was prepared by the following method.

[Production of compound containing antistatic agent] HI
The copolymer (C-1) of the PS resin (R-1), the styrene monomer and the acid group-containing vinyl compound and the polyetherester (S-1) were each 74/6/20 by weight. The mixture was kneaded with a twin-screw extruder and pelletized to obtain an antistatic resin composition.

[Production of Comparative Surfactant-Containing Resin Component]
HIPS resin (R-1) and surfactant-containing masterbatch (containing 20% by weight of alkyldiethanolamine,
"K0554E" manufactured by Hexa Chemical Co., Ltd.) was dry-blended at a ratio of 90/10 on a weight basis.

[Production of Comparative Conductive Filler-Containing Resin Component] The HIPS resin J-2, the hydrogenated styrene-butadiene block copolymer J-3 and the carbon black were each in a proportion of 60/15/25 (weight ratio). What was added in
The mixture was kneaded with a Banbury mixer and pelletized to obtain a compound containing a conductive filler. Then, this is R-
1 and [conductive filler-containing compound] / [R-
1] = 60/40 dry blended, carbon concentration 1
5% by weight of the composition was obtained. This

Examples 1 to 11 and Comparative Examples 1 to 4 Resins and layers shown in Tables 1 to 8
mm and 65 mm diameter extruder, feed block, T
The film was formed by a co-extrusion method using a sheet manufacturing apparatus including a die and a take-off machine. A 50 mm extruder was used as an antistatic agent-containing thermoplastic resin layer (B), and a 65 mm extruder was used as a thermoplastic resin layer (A).
As 0 ° C, laminate in a 210 ° C feedblock,
From the T-die having a lip opening of 0.7 mm, a two- and three-layer sheet having a thickness of 0.5 mm was formed. The obtained laminated sheet layer ratio was 10/80/10. In addition, single layer sheet is 65m
A film was formed in the same manner using only an extruder having a diameter of m.

[0122]

[Table 1]

[0123]

[Table 2]

[0124]

[Table 3]

[0125]

[Table 4]

[0126]

[Table 5]

[0127]

[Table 6]

[0128]

[Table 7]

[0129]

[Table 8]

[0130]

According to the present invention, molding into a complicated shape or a deep drawing shape is easy, and it is particularly useful in electronic device tray applications, and at the same time, the conductive performance due to interruption of a conductive path and the like is reduced. An object of the present invention is to provide an antistatic sheet which is free from contamination and does not further cause contamination of contents, a method for producing the same, and a molded product obtained from the sheet. Therefore,
The antistatic sheet of the present invention is suitable for packaging electronic parts such as carrier tapes and trays.

 ──────────────────────────────────────────────────の Continued on the front page F-term (reference) 4F100 AK12A AK12B AK12C AK12J AK25B AK25C AK25J AK41B AK41C AK41H AL01B AL01C AL05A AL05B AL05C AL07B AL07C AN00A AN00B AN00C BA02 BA04 J04 BA07 BA10G BAC JK07 JN01 YY00B YY00C 4J002 BC03W BC04Y BC07W BN14W BN15W BN16W CH05X

Claims (13)

[Claims] 1. An antistatic property having a structure in which a styrene resin layer (A) and a styrene resin layer (B) containing a polyetherester antistatic agent (b1) are laminated. Laminated sheet. 2. The compounding ratio of the polyetherester antistatic agent (b1) in the styrene resin layer (B) is 2 to 40.
The sheet according to claim 1, which is in weight%. 3. A laminated sheet comprising a styrene resin layer (A)
The antistatic laminate sheet according to claim 1 or 2, wherein a styrenic resin layer (B) containing a persistent antistatic agent is laminated on both surfaces of the laminate. 4. The antistatic laminate sheet according to claim 1, wherein the styrene resin layer (B) has a surface resistance of 10 ⁹ Ω to 10 ¹³ Ω. 5. The styrene-based resin layer (A) comprises a styrene-based resin (a1) as a main component.
5. The antistatic laminate sheet according to any one of 4. 6. The antistatic laminate sheet according to claim 5, wherein a rubbery styrene resin is used as the styrene resin (a1). 7. The styrene resin layer (B) contains a polyetherester antistatic agent (b1) and a styrene resin (b2) as essential components. The antistatic laminated sheet according to one of the above. 8. The antistatic laminated sheet according to claim 7, wherein a rubbery styrene resin is used as the styrene resin (b2). 9. The styrene resin layer (B) further comprises a copolymer (b3) of a styrene monomer and an acid group-containing vinyl compound in addition to (b1) and (b2). 1 to
8. The antistatic laminate sheet according to any one of 8. 10. A copolymer (b) of a styrene monomer and an acid group-containing vinyl compound in the styrene resin layer (B).
The antistatic laminated sheet according to claim 9, wherein the content of 3) is in the range of 1 to 30% by weight. 11. A styrene resin (a1) is melt-kneaded and a polyetherester antistatic agent (b1) is used.
And a styrene-based resin (b2) by melt-kneading, co-extruding the two, and forming a film. 12. A styrene resin (a1) is melt-kneaded and a polyetherester antistatic agent (b1) is used.
And the styrene-based resin (b2) are melt-kneaded, and both are co-extruded to obtain a [styrene-based resin layer containing a polyetherester-based antistatic agent (B) / styrene-based resin layer (A) /
The styrenic resin layer containing a polyetherester-based antistatic agent (B)]. 13. A molded article obtained by molding the antistatic sheet according to any one of claims 1 to 10.