JP4875323B2 - Antistatic resin composition and molded article - Google Patents

Description

  The present invention relates to an antistatic resin composition excellent in antistatic property, impact resistance, and appearance of a molded product, and a molded product comprising the antistatic resin composition.

Styrenic resins such as ABS resin are excellent in impact resistance, molded product surface appearance and moldability, so they can be used in the electrical / electronic field, OA / home appliance field, building material field, toy field, sanitary field, vehicle field, etc. Widely used. However, since such styrenic resins are easily charged and cause problems of static electricity damage, they are used in various parts, sheets, films, etc. used in liquid crystal display devices, semiconductor peripheral devices, plasma displays, clean rooms, etc. It was difficult to use. For the purpose of preventing chargeability of styrene resins such as ABS resin, Patent Document 1, Patent Document 2, and Patent Document 3 disclose compositions in which a polyamide elastomer is blended with a rubber-reinforced styrene resin. Although this technique improves the antistatic property of the molded product, it is not sufficient. For example, when a molded product is obtained by injection molding, the antistatic property is exhibited near the gate, but the antistatic property is inferior at the flow end. Also, when extrusion molding is performed to obtain a sheet, film, etc., there are problems such as poor antistatic properties.

Japanese Patent Laid-Open No. 63-23435 JP-A-4-309547 JP-A-2-292353

  The objective of this invention is providing the antistatic resin composition excellent in antistaticity, impact resistance, and the external appearance of a molded article. Another object of the present invention is to provide the molded article.

As a result of intensive studies to achieve the above-mentioned object, the present inventors have further specified a composition in which a block copolymer having a polyamide block and / or a polyester block and a hydrophilic polymer block is blended with a styrenic resin. It has been found that by adding a fluorinated alkyl sulfonate and / or a nonionic surfactant as a compound, a molded product excellent in antistatic property, impact resistance and appearance of the molded product can be obtained. It was completed.
That is, according to one aspect of the present invention,
(A) A rubber-reinforced styrene resin (A1) obtained by polymerizing a vinyl monomer (b) containing an aromatic vinyl compound in the presence of a rubbery polymer (a) and / or the vinyl 70 to 97% by mass of a styrene-based resin comprising a (co) polymer (A2) of the monomer (b),
(B) 3 to 30% by mass of a block copolymer having a polyamide and / or polyester block (B1) and a hydrophilic polymer block (B2),
It contains the component (A) and the component (B) (however, the total of the component (A) and the component (B) is 100% by mass),
Furthermore, at least 1 selected from the group consisting of (C) fluorinated alkyl sulfonate (C1) and nonionic surfactant (C2) with respect to a total of 100 parts by mass of component (A) and component (B). An antistatic resin composition comprising 0.01 to 10 parts by mass of a seed is provided.

  According to the present invention, (A) a styrenic resin (sometimes referred to herein as “component (A)”) and (B) a polyamide and / or polyester block and a hydrophilic polymer block. A resin composition blended with a block copolymer (sometimes referred to as “component (B)” in this specification) is added to (C) a fluorinated alkyl sulfonate (in this specification, “component (B)”. C1) ”and at least one selected from the group consisting of nonionic surfactants (also referred to herein as“ component (C2) ”) (herein“ Component (C) ").), The molded product having excellent antistatic properties, impact resistance and molded product appearance can be obtained by using the resin composition.

  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.

Ingredient (A)
Component (A) of the present invention is a rubber-reinforced styrene resin (A1) obtained by polymerizing a vinyl monomer (b) containing an aromatic vinyl compound in the presence of a rubbery polymer (a). And / or (co) polymer (A2) obtained by (co) polymerizing this vinyl monomer (b). The latter (co) polymer (A2) is obtained by polymerizing a vinyl monomer (b) containing an aromatic vinyl compound in the absence of the rubbery polymer (a). These resins can be used alone or in combination of two or more. Hereinafter, each of the component (A1) and the component (A2) will be described in detail.

Ingredient (A1)
The rubber-reinforced styrene resin (A1) is obtained by polymerizing a vinyl monomer (b) containing an aromatic vinyl compound in the presence of the rubbery polymer (a).
The rubbery polymer (a) includes polybutadiene, butadiene / styrene copolymer, butadiene / acrylonitrile copolymer, styrene / butadiene block copolymer and hydrogenated product thereof, styrene / isoprene block copolymer and Diene rubber such as hydrogenated products; ethylene / propylene copolymer, ethylene / propylene / non-conjugated diene copolymer, ethylene / butene-1 copolymer, ethylene / butene-1 / non-conjugated diene copolymer, etc. Examples include ethylene / α-olefin rubbers; acrylic rubbers; silicone rubbers; silicone / acrylic IPN rubbers and the like. These polymers can be used singly or in combination of two or more.
Among these, hydrogen of polybutadiene, butadiene / styrene copolymer, ethylene / propylene copolymer, ethylene / propylene / nonconjugated diene copolymer, styrene / butadiene block copolymer, styrene / butadiene block copolymer. Additives and acrylic rubber are preferred.

When the rubbery polymer (a) is obtained by emulsion polymerization, the gel content is preferably 98% by mass or less, and more preferably 40 to 98% by mass. By setting it as this range, the antistatic resin composition which gives the molded article excellent in impact resistance can be obtained.
The gel content can be determined by the following method.
First, 1 g of a rubbery polymer is put into 100 ml of toluene and allowed to stand at room temperature for 48 hours. Thereafter, the toluene-insoluble matter and the wire mesh filtered through a 100-mesh wire mesh (mass is W ₁ gram) are vacuum-dried at a temperature of 80 ° C. for 6 hours and weighed (mass W is ₂ grams). Substituting W ₁ and W ₂ into the following formula (1) to obtain the gel content.
Gel content = [{W ₂ (g) −W ₁ (g)} / 1 (g)] × 100 (1)

  The gel content is set appropriately at the time of production of the rubbery polymer, such as the type and amount of the crosslinkable monomer, the type and amount of the molecular weight regulator, the polymerization time, the polymerization temperature, and the polymerization conversion rate. It is adjusted by doing.

  The vinyl monomer (b) polymerized in the presence of the rubbery polymer may be composed only of the aromatic vinyl compound, or can be copolymerized with the aromatic vinyl compound. It may be composed of other vinyl monomers. Other vinyl monomers that can be copolymerized include vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, acid anhydride groups, hydroxyl groups, amino groups, epoxy groups, carboxyl groups, Examples thereof include vinyl compounds containing a functional group such as an oxazoline group.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, hydroxystyrene and the like. These compounds can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are preferred. The amount of the aromatic vinyl compound used is preferably 10 to 100% by mass, more preferably 10 to 90% by mass, and still more preferably 10 to 80% by mass, based on 100% by mass of the total amount of the vinyl monomer (b). It is. When it is in this range, the physical properties balance between molding processability and mechanical strength is excellent.

  Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. These compounds can be used alone or in combination of two or more. Of these, acrylonitrile is preferred. When a vinyl cyanide compound is used, the amount used is preferably 50% by mass or less, more preferably 5 to 40% by mass, based on 100% by mass of the total amount of the vinyl monomer (b). Within this range, the chemical properties, color tone and molding processability are excellent in physical property balance.

  Examples of the (meth) acrylic acid ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and the like. These compounds can be used alone or in combination of two or more. Of these, methyl methacrylate is preferred. When a (meth) acrylic acid ester compound is used, the amount used is preferably 90% by mass or less, more preferably 10 to 85% by mass, particularly 100% by mass based on the total amount of the vinyl monomer (b). Preferably it is 50-85 mass%. When in this range, the balance of colorability, transparency, moldability, etc. is excellent.

  Examples of the maleimide compound include maleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like. These compounds can be used alone or in combination of two or more. As a method for introducing the maleimide compound unit into the molecule, a method of copolymerizing maleic anhydride and then imidizing it may be used. When a maleimide compound is used, the amount used is preferably 50% by mass or less, more preferably 10 to 50% by mass, based on 100% by mass of the total amount of the vinyl monomer (b). Within this range, the physical property balance between heat resistance and moldability is excellent.

  Examples of the vinyl compound containing an acid anhydride group include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These compounds can be used alone or in combination of two or more.

  Examples of vinyl compounds having a hydroxyl group include 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, and 3-hydroxy- Examples include 2-methyl-1-propene, hydroxystyrene, 2-hydroxyethyl (meth) acrylate, and N- (4-hydroxyphenyl) maleimide. These compounds can be used alone or in combination of two or more.

  Examples of the vinyl compound having an amino group include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, phenylaminoethyl (meth) acrylate, N-vinyldiethylamine, N -Acetyl vinylamine, (meth) acrylamine, N-methylacrylamine, (meth) acrylamide, N-methylacrylamide, p-aminostyrene, etc. are mentioned. These compounds can be used alone or in combination of two or more.

  Examples of the vinyl compound having an epoxy group include glycidyl (meth) acrylate, 3,4-oxycyclohexyl (meth) acrylate, vinyl glycidyl ether, acryl glycidyl ether, and methacryl glycidyl ether. These compounds can be used alone or in combination of two or more.

Examples of the vinyl compound having a carboxyl group include (meth) acrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid and the like. These compounds can be used alone or in combination of two or more.
Examples of the vinyl compound containing an oxazoline group include vinyl oxazoline. These compounds can be used alone or in combination of two or more.

The vinyl compound containing a functional group such as an acid anhydride group, a hydroxyl group, an amino group, an epoxy group, a carboxyl group, or an oxazoline group (hereinafter sometimes referred to as “specific functional group-containing vinyl compound”) is used. In this case, when the styrene resin and another polymer are blended, the compatibility between the two can be improved. Preferred monomers for achieving such effects are epoxy group-containing unsaturated compounds, unsaturated acid compounds, and hydroxyl group-containing unsaturated compounds, particularly preferably hydroxyl group-containing unsaturated compounds.
When such a specific functional group-containing vinyl compound is used, the amount used is preferably 20% by mass or less, more preferably 1 to 15% by mass, based on 100% by mass of the total amount of the vinyl monomer (b). is there. When it is in this range, it is excellent in the balance of compatibility imparting effect and appearance of the molded product.

A preferable combination of the monomers constituting the vinyl monomer (b) is divided into a case where the vinyl monomer (b) contains a specific functional group-containing vinyl compound and a case where it does not contain, Shown below.
[When the vinyl monomer (b) does not contain a specific functional group-containing vinyl compound]
(1) A vinyl monomer (b) comprising an aromatic vinyl compound.
(2) A vinyl monomer (b) comprising at least two selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound, a (meth) acrylic acid ester compound and a maleimide compound.
(3) A vinyl monomer (b) comprising an aromatic vinyl compound and a vinyl cyanide compound.
(4) A vinyl monomer (b) comprising an aromatic vinyl compound, a (meth) acrylic acid ester compound and a vinyl cyanide compound.
(5) A vinyl monomer (b) comprising an aromatic vinyl compound and a (meth) acrylic acid ester compound.
(6) A vinyl monomer (b) comprising an aromatic vinyl compound and a maleimide compound.
[When the vinyl monomer (b) contains a specific functional group-containing vinyl compound]
(1) A vinyl monomer (b) comprising an aromatic vinyl compound and a specific functional group-containing vinyl compound.
(2) A vinyl monomer comprising an aromatic vinyl compound, at least two selected from the group consisting of a vinyl cyanide compound, a (meth) acrylic acid ester compound and a maleimide compound, and a specific functional group-containing vinyl compound. (B).
(3) A vinyl monomer (b) comprising an aromatic vinyl compound, a vinyl cyanide compound, and a specific functional group-containing vinyl compound.
(4) A vinyl monomer (b) comprising an aromatic vinyl compound, a (meth) acrylic acid ester compound, and a specific functional group-containing vinyl compound.
(5) A vinyl monomer (b) comprising an aromatic vinyl compound, a maleimide compound, and a specific functional group-containing vinyl compound.
The vinyl monomer (b) is preferably composed of two or more different monomers, and more preferred combinations are shown below. In addition, the number in parentheses is a preferable use ratio (unit: mass%) when the total of both is 100 mass%.
(1) Aromatic vinyl compound / vinyl cyanide compound (65 to 90/35 to 10).
(2) Aromatic vinyl compound / methyl methacrylate (20-80 / 80-20).
(3) Aromatic vinyl compound / vinyl cyanide compound / methyl methacrylate (10-80 / total of the latter two is 90-20).
(4) Aromatic vinyl compound / maleimide compound (50 to 90/50 to 10).
(5) Aromatic vinyl compound / methyl methacrylate / maleimide compound (10-80 / total of the latter two is 90-20).
(6) Aromatic vinyl compound / vinyl cyanide compound / glycidyl methacrylate (64.9-89.9 / 10-35 / 0.1-20).
(7) Aromatic vinyl compound / vinyl cyanide compound / (meth) acrylic acid (64.9-89.9 / 10-35 / 0.1-20).
(8) Aromatic vinyl compound / vinyl cyanide compound / 2-hydroxyethyl methacrylate (10 to 80 / total of the latter two is 90 to 20).
(9) Aromatic vinyl compound / maleic anhydride (80-99.9 / 20-0.1).

  The rubber-reinforced styrene resin (A1) can be produced by a known polymerization method, for example, emulsion polymerization, bulk polymerization, solution polymerization, suspension polymerization, or a polymerization method combining these. Of these, emulsion polymerization, solution polymerization, and suspension polymerization are preferred.

When the rubber-reinforced styrene resin (A1) is produced by emulsion polymerization, a polymerization initiator, a chain transfer agent, an emulsifier and the like are usually used. Any of these 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, it is preferable to use redox systems such as various reducing agents, sugar-containing iron pyrophosphate formulations, sulfoxylate formulations, etc., as polymerization initiation assistants.

Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan and n-hexyl mercaptan; terpinolenes and the like.
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 Examples thereof include rosinates such as potassium and dialkylsulfosuccinates such as sodium dioctylsulfosuccinate.

When the rubber-reinforced styrene resin (A1) is produced by emulsion polymerization, the rubbery polymer (a) and the vinyl monomer (b) are used in the presence of the entire amount of the rubbery polymer (a). The vinyl monomer (b) may be added and polymerized all at once, or may be polymerized by divided addition or continuous addition. Moreover, you may add a part of rubber-like polymer (a) in the middle of superposition | polymerization.
When 100 parts by mass of the rubber-reinforced styrene resin (A1) is produced, the amount of the rubbery polymer used is preferably 3 to 80 parts by mass, more preferably 5 to 70 parts by mass, and still more preferably 10 to 60 parts. Part by mass.

  The latex obtained by emulsion polymerization is usually subjected to coagulation of the resin component with a coagulant, and further washed with water and dried to obtain a purified rubber-reinforced styrene resin (A1). As the coagulant, inorganic salts such as calcium chloride, magnesium sulfate and magnesium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid, citric acid and malic acid can be used. When two or more types of latex are produced, the coagulation may be performed separately for each latex, or may be performed after mixing two or more types of latex.

When the rubber-reinforced styrene resin (A1) is produced by solution polymerization, the polymerization is usually performed in a known inert polymerization solvent for radical polymerization. Examples of the solvent include aromatic hydrocarbons such as ethylbenzene and toluene; ketones such as methyl ethyl ketone and acetone; acetonitrile, dimethylformamide, N-methylpyrrolidone and the like.
The polymerization temperature is preferably in the range of 80 to 140 ° C, more preferably 85 to 120 ° C.

In solution polymerization, a polymerization initiator may be used, or polymerization may be performed by thermal polymerization without using a polymerization initiator. Examples of the polymerization initiator include azo compounds such as azobisisobutyronitrile; organic peroxides such as ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxy ester, hydroperoxide, and benzoyl peroxide. Preferably used.
When a chain transfer agent is used, mercaptans; terpinolenes; α-methylstyrene dimer, etc. can be used.
Moreover, when manufacturing rubber reinforcement | strengthening styrene-type resin (A1) by block polymerization or suspension polymerization, a well-known method can be applied and the polymerization initiator, chain transfer agent, etc. which were illustrated to solution polymerization can be used.
The content of the vinyl monomer remaining in the rubber-reinforced styrene-based resin (A1) obtained by each polymerization method is preferably 10,000 ppm or less, and more preferably 5,000 ppm or less.

  The rubber-reinforced styrenic resin (A1) produced as described above is usually a graft copolymer obtained by grafting (co) polymerizing a vinyl monomer (b) to a rubbery polymer (a). And an ungrafted copolymer that is not grafted to the rubber polymer (substantially the same as the (co) polymer (A2)).

The graft ratio of the rubber-reinforced styrene resin (A1) is preferably 20 to 200% by mass, more preferably 30 to 150% by mass, and still more preferably 40 to 120% by mass. When the graft ratio is in the above range, the impact resistance is excellent.
The graft rate can be determined by the following method.
Graft ratio (mass%) = {(TS) / S} × 100 (2)
In the above formula (2), T is 1 g of component (A1) in 20 ml of acetone (but acetonitrile if the rubbery polymer (a) uses acrylic rubber), and 2 by a shaker. It is the mass (g) of insoluble matter obtained by centrifuging for 60 minutes in a centrifuge (rotation speed: 23,000 rpm) after shaking for a while to separate the insoluble matter and the soluble matter. (A1) The mass (g) of the rubbery polymer contained in 1 g.

Intrinsic viscosity [η] (soluble in methyl ethyl ketone as a solvent) of acetone of rubber-reinforced styrene resin (A1) (but acetonitrile if rubbery polymer (a) uses acrylic rubber) , Measured at 30 ° C.) is preferably 0.2 to 1.2 dl / g, more preferably 0.2 to 1.0 dl / g, and particularly preferably 0.3 to 0.8 dl / g. When the intrinsic viscosity [η] is in this range, the balance of impact resistance, workability, and molded product appearance is excellent.
The number average particle size of the graft copolymer dispersed in the component (A1) is preferably 500 to 30,000, more preferably 1,000 to 20,000, and still more preferably 1,500 to 8,000. It is a range. The number average particle diameter can be measured by a known method such as using an electron microscope.

  The graft ratio, intrinsic viscosity [η] and the above number average particle size are the types and amounts of polymerization initiators, chain transfer agents, emulsifiers, solvents, etc. used in producing the rubber-reinforced styrene resin (A1). Furthermore, it can be easily controlled by changing the polymerization time, polymerization temperature and the like.

Ingredient (A2)
The (co) polymer (A2) is obtained by (co) polymerizing the vinyl monomer (b) in the absence of the rubbery polymer (a). It can be produced by the same method as the component (A1) except that the (co) polymerization of the body (b) is carried out in the absence of the rubbery polymer (a). All the vinyl monomers (b) listed for the component (A1) can be used for the production of the (co) polymer (A2). Moreover, the preferable usage-amount of the said vinylic monomer (b) corresponds also about (co) polymer (A2).
When this (co) polymer (A2) is used in combination with the rubber-reinforced styrene resin (A1), the vinyl used in the production of the rubber-reinforced styrene resin (A1) as the (co) polymer (A2). (Co) polymers obtained using the same type of compound as the system monomer may be used, or (co) polymers obtained using a different type of compound may be used. .

  The (co) polymer (A2) can be produced by a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization.

The intrinsic viscosity [η] of the (co) polymer (A2) (measured at 30 ° C. using methyl ethyl ketone as a solvent) 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. When the intrinsic viscosity [η] is in this range, the balance between workability and appearance of the molded product is excellent.
The intrinsic viscosity [η] can be controlled by changing various production conditions as in the case of the rubber-reinforced styrene resin (A1).

The component (A) of the present invention may comprise only one of the rubber-reinforced styrene resin (A1) and the (co) polymer (A2), and the rubber-reinforced styrene resin (A1) and ( It may be composed of both of the (co) polymer (A2). However, the component (A) may contain both the rubber-reinforced styrene resin (A1) and the (co) polymer (A2) in order to stably exhibit impact resistance and antistatic properties. preferable.
The content of the rubber-like polymer (a) in the component (A) is preferably 2 to 40% by mass, more preferably 3 to 35% by mass, based on 100% by weight of the whole component (A). When the content of the rubbery polymer (a) is within this range, the impact resistance, molding processability, and rigidity are excellent in balance of physical properties.
The content of the vinyl monomer (b) in the component (A) is preferably 60 to 98% by mass, more preferably 65 to 97% by mass, based on 100% by weight of the whole component (A). When the content of the vinyl monomer (b) is in this range, the balance of physical properties of impact resistance, molding processability and rigidity is excellent. For the purpose of improving the affinity between the component (A) and the component (B) of the present invention, the component (A) is a component (A1) or a component containing the specific functional group-containing vinyl compound as a copolymer component. It is preferable that (A2) is included. In this case, the specific functional group-containing vinyl compound constitutes 0.1 to 20% by mass of the entire vinyl monomer (b) (100% by weight) constituting the component (A1) or the component (A2). It is preferable. The content of the component (A1) or component (A2) containing the specific functional group-containing vinyl compound as a copolymerization component is 0.3 to 30% by mass relative to the entire component (A) (100% by mass). Is preferable, more preferably 0.5 to 20% by mass, and particularly preferably 1 to 15% by mass. When the content is within this range, the impact resistance and the appearance of the molded product are excellent.

  In the antistatic resin composition of the present invention, the amount of the component (A) used is 70 to 97% by mass, preferably 75 when the total of the component (A) and the component (B) is 100% by mass. It is -95 mass%, More preferably, it is 77-95 mass%, Most preferably, it is 78-94 mass%. If the amount used is less than 70% by mass, the impact resistance and the appearance of the molded product tend to be inferior. On the other hand, if it exceeds 97% by mass, the antistatic property is inferior.

Ingredient (B)
The component (B) of the present invention is a block copolymer having a polyamide and / or polyester block (B1) and a hydrophilic polymer block (B2).
The component (B) of the present invention includes a diblock copolymer of a polyamide block (B1-a) and a hydrophilic polymer block (B2), a multiblock copolymer, a polyester block (B1-b) and a hydrophilic block. Diblock copolymer with hydrophilic polymer block (B2), and block copolymer of multi-block copolymer, block (B1-c) comprising polyamide block and polyester block and hydrophilic polymer block (B2) And a block copolymer of a block copolymer (B1-d) comprising a mixture of the block copolymers (B1-a) to (B1-c) and a hydrophilic polymer block (B2). From the viewpoint of antistatic properties, (B1-a) and (B1-b) are preferred as (B1), and (B1-a) is more preferred.

  Polyamides used in (B1-a) include ethylenediamine, tetramethylenediamine, hexamethylenediamine, decamethylenediamine, 2,3,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- or A diamine component such as 1,4-bis (aminomethyl) cyclohexane, bis (p-aminohexyl) methane, phenyldiamine, m-xylenediamine, and p-xylenediamine; Ring-opening polymerization of lactams such as polyamide, caprolactam, lauryl lactam derived from aliphatic, alicyclic or aromatic dicarboxylic acids such as adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid Polyamide selected by There are polyamides derived from aminocarboxylic acids such as ω-aminocaproic acid, ω-aminoenanoic acid, aminoundecanoic acid, and 1,2-aminododecanoic acid, and copolyamides thereof, and further mixed polyamides thereof.

  The polyester in (B1-b) is a polymer obtained from (1) a dicarboxylic acid component having 4 to 20 carbon atoms and / or an ester-forming derivative thereof and (2) a diol component. Examples of (1) used here are as follows. Here, the number of carbons refers to the total number of carbons constituting a chain or ring directly connected to the carbon of the carboxyl group and the carbon of the carboxyl group.

  Examples of the dicarboxylic acid having 4 to 20 carbon atoms include (a) 4 to 20 carbon atoms such as succinic acid, adipic acid, azelaic acid, sebacic acid, α, ω-dodecanedicarboxylic acid, dodecenyl succinic acid, octadecenyl dicarboxylic acid, and the like. (B) 1,4-cyclohexanedicarboxylic acid and other aliphatic dicarboxylic acids having 8 to 20 carbon atoms, (c) terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3 -Aromatic dicarboxylic acid having 8 to 12 carbon atoms such as naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, (d) 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, Substituted aromatic dicarboxylic acids having 8 to 12 carbon atoms in which a sulfonic acid group such as 5-tetrabutylphosphonium sulfoisophthalic acid is bonded to an aromatic ring A carboxylic acid etc. are mentioned. Examples of the ester-forming derivative of a C 4-20 dicarboxylic acid include the lower alkyl esters (a) to (b). For example, dimethyl succinate, dimethyl adipate, dimethyl azelate, dimethyl sebacate, dimethyl α, ω-dodecanedicarboxylate, dimethyl dodecenyl succinate, dimethyl octadecenyl dicarboxylate, dimethyl 1,4-cyclohexanedicarboxylate , Diethyl succinate, diethyl adipate, diethyl azelate, diethyl sebacate, diethyl α, ω-dodecanedicarboxylate, diethyl dodecenyl succinate, diethyl octadecenyl dicarboxylate, diethyl 1,4-cyclohexanedicarboxylate, dimethyl terephthalate , Diethyl terephthalate, di (2-hydroxyethyl) terephthalate, dimethyl 1,4-naphthalenedicarboxylate, diethyl 1,4-naphthalenedicarboxylate, dimethyl 2,6-naphthalenedicarboxylate , Diethyl 2,6-naphthalenedicarboxylate, dimethyl 2,7-naphthalenedicarboxylate, diethyl 2,7-naphthalenedicarboxylate, 5-sodium sulfoisophthalic acid (2-hydroxyethyl), 5-potassium sulfoisophthalic acid (2- Hydroxyethyl) and the like. These may be used alone or in combination of two or more. Among these, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid and ester forming derivatives thereof are preferable.

  Examples of the diol component used in (B1-b) include ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, diethylene glycol, 1,1-cyclohexanedimethylol, 1 , 4- and 1,3-cyclohexanedimethylol, 2,2-bis (4′-β-hydroxyethoxyphenyl) propane, bis (4′-β-hydroxyethoxyphenyl) sulfonic acid and the like. One species can be used alone, or two or more species can be used in combination. Of these, ethylene glycol and tetramethylene glycol are preferable.

Examples of the hydrophilic polymer block (B2) include polyether (b2-a), polyether-containing hydrophilic polymer (B2-b), and anionic polymer (B2-c).
Examples of the polyether (B2-a) include polyether diol, polyether diamine, and modified products thereof.
Examples of the polyether-containing hydrophilic polymer (B2-b) include polyether ester amide having a polyether diol segment, polyether amide imide having a polyether diol segment, polyether ester having a polyether diol segment, Examples include polyether amides having ether diamine segments, and polyether urethanes having polyether diol or polyether diamine segments.
As the anionic polymer (B2-c), a dicarboxylic acid having a sulfonyl group and a polyether (B2-a) are essential structural units, and preferably 2 to 80, more preferably 3 to 3 in one molecule. Examples include anionic polymers having 60 sulfonyl groups.
These may be linear or branched. Particularly preferred component (B2) is polyether (B2-a).

As the polyether diol in the polyether (B2-a), the general formula (3):
H— (OA ¹ ) _n —O—E ¹ —O— (A ¹ O) _{n ′} —H, and general formula (4):
H- (OA ² ) _m —O—E ² —O— (A ² O) _{m ′} —H are exemplified.
In general formula (3), 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 in the case where these are composed of two or more oxyalkylene groups May be either block or random or a combination thereof. n and n ′ are generally integers of 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, and urushiol, bisphenol A, bisphenol F, bisphenol S, 4,4'-dihydroxydiphenyl-2,2-butane, dihydroxybiphenyl, and dihydroxydiphenyl ether. And condensed polycyclic dihydric phenols such as dihydroxynaphthalene and binaphthol.

In the general formula (4), E ² is a residue obtained by removing a hydroxyl group from the divalent hydroxyl group-containing compound described in the general formula (3), and A ² is at least partly a general formula (5): —CHR— CHR ′ — [wherein one of R and R ′ is a group represented by general formula (6): —CH ₂ O (A ³ O) _X R ″, and the other is H. General formula (6) Wherein x is an integer of 1 to 10, R ″ is H or an alkyl group, aryl group, alkylaryl group, arylalkyl group or acyl group having 1 to 10 carbon atoms, and A ³ is an alkylene group having 2 to 4 carbon atoms. It is. The remaining alkylene group may be an alkylene group having 2 to 4 carbon atoms. 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 (3) 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 alkylene oxides are 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 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 (4) include the following methods (a) and (b).
(A) General formula (7): Starting from the above divalent hydroxyl group-containing compound

[A ⁴ in the general formula (7) is an alkylene group having 2 to ⁴ carbon atoms, p is an integer of 1 to 10, R ¹ is H or an alkyl group having 1 to 10 carbon atoms, an aryl group, an 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.

Examples of the alkylene oxide having 2 to 4 carbon atoms used here include those described above.
Moreover, the preferable component (B) of this invention can be obtained by superposing | polymerizing said (B1) and (B2) by a well-known method. For example, the block (B1) and the block (B2) can be produced by performing a polymerization reaction at 200 to 250 ° C. under reduced pressure.

  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.

A preferred polymerization method for the polyamide block (B1-a) is a heat melt polymerization method, and specific examples of preferred polymerization methods for the component (B) using (B1-a) are shown below.
(I) A method in which, after polymerizing polyamide, a dicarboxylic acid compound is added, both ends of the polyamide component are carboxylated, and poly (alkylene oxide) glycol is added and polymerized to obtain a block copolymer.
(Ii) A method in which a dicarboxylic acid compound is excessively added and polymerized so that molecular end groups are substantially carboxylated during polyamide polymerization, and further poly (alkylene oxide) glycol is added and polymerized to obtain a block copolymer.
(Iii) A method of obtaining a block copolymer by adding a specified amount of a polyamide-forming component, an excess of a dicarboxylic acid compound, and poly (alkylene oxide) glycol all at once.

Dicarboxylic acids used to carboxylate the molecular ends of the polyamide include adipic acid, suberic acid, sebacic acid, maleic acid, citraconic acid, maleic anhydride, citraconic anhydride, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid Etc. In order to achieve the object of the present invention, the number average molecular weight of the polyamide of the present invention is preferably in the range of 500 to 20,000, more preferably 500 to 10,000, and particularly preferably 500 to 5,000. Is preferable.
The mass ratio (B1-a) / (B2) of the polyamide block (B1-a) and the hydrophilic polymer block (B2) in the component (B) of the present invention may be in the range of 90/10 to 10/90. The ratio is more preferably 80/20 to 20/80, and particularly preferably 70/30 to 30/70.

The molecular weight of the component (B) using a polyamide block for (B1) is not particularly limited, but the reduced viscosity (ηsp / C) (measured in formic acid solution at 0.5 g / 100 ml at 25 ° C.) is: It is preferably in the range of 1.0 to 3.0 dl / g, more preferably 1.2 to 2.5 dl / g.
Furthermore, (B1-a) of this invention can be used individually by 1 type or in combination of 2 or more types.
Particularly preferred is a polyether ester amide in which a polyamide and a poly (alkylene oxide) glycol block are linked by an ester bond, and can be obtained as Sanyo Kasei Kogyo's Pelestat NC6321, M-140, 6500 (trade name).

A preferred polymerization method for the polyester block (B1-b) is a heat melt polymerization method, and specific examples of preferred polymerization methods for the component (B) using (B1-b) are shown below.
(I) A method of polymerizing a polyester, then adding a dicarboxylic acid compound, carboxylating both ends of the polyester component, and adding and polymerizing poly (alkylene oxide) glycol to obtain a block copolymer.
(Ii) A method in which a dicarboxylic acid compound is excessively added and polymerized so that both molecular ends are substantially carboxylated during polyester polymerization, and poly (alkylene oxide) glycol is further added and polymerized to obtain a block copolymer.
(Iii) A method of obtaining a block copolymer by adding a specified amount of a polyester-forming component, an excess of a dicarboxylic acid compound, and poly (alkylene oxide) glycol all at once.

As the dicarboxylic acid used for carboxylating the molecular terminal of the polyester, all of the above-mentioned ones can be used. The number average molecular weight of the polyester used in the present invention is preferably 300 to 20,000, more preferably 300 to 10,000, and particularly preferably 500 to 5,000 to achieve the object of the present invention. Preferred above.
The mass ratio (B1-b) / (B2) of the polyester block (B1-b) and the hydrophilic polymer block (B2) in the component (B) of the present invention may be in the range of 90/10 to 10/90. The ratio is more preferably 80/20 to 20/80, and particularly preferably 70/30 to 30/70.

The molecular weight of the component (B) using the polyester block (B1-b) in the block (B1) is not particularly limited, but the reduced viscosity (ηsp / C) (phenol / tetrachloroethane = 40/60 mass ratio) Using a mixed solvent, the concentration is 1.0 g / dl and measured at 35 ° C.) is preferably in the range of 0.3 to 2.5 dl / g, more preferably 0.5 to 2.5 dl / g. is there.
Furthermore, (B1-b) of this invention can be used individually by 1 type or in combination of 2 or more types.
As such a component (B) containing (B1-b), it can obtain as TEP004, TEP010, TEP008 (brand name) by Takemoto Yushi Co., Ltd., for example.

Known antioxidants, heat stabilizers, and the like may be present during the production of the component (B) of the present invention (before polymerization, during polymerization, and after polymerization).
Further, for the purpose of further improving the antistatic property, which is the object of the present invention, a salt (D) of an alkali metal and / or alkaline earth metal (also referred to as “component (D)” in the present specification). Can be contained. These components can be contained before the polymerization of the component (B) and during the polymerization of the component (B), or can be contained after the polymerization of the component (B). The antistatic resin composition of the present invention can also be contained. It can mix | blend at the time of manufacture, and can also be made to contain by the method which combined these.
Examples of the component (D) 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 component (D) include halides of alkali metals such as lithium chloride, sodium chloride, potassium chloride, lithium bromide, sodium bromide, potassium bromide; sodium perchlorate, potassium perchlorate, etc. Alkali metal inorganic acid salts, alkali metal organic acid salts such as potassium acetate and lithium stearate; octyl sulfonic acid, dodecyl sulfonic acid, tetradecyl sulfonic acid, stearyl sulfonic acid, tetracosyl sulfonic acid, 2-ethylhexyl sulfone Alkali metal salt of alkyl sulfonic acid having 8 to 24 carbon atoms of alkyl group such as acid; Alkali metal salt of aromatic sulfonic acid such as phenyl sulfonic acid and naphthyl sulfonic acid; Octyl phenyl sulfonic acid, dodecyl phenyl sulfonic acid, dibutyl Phenylsulfonic acid, dinonylphenyl Alkali metal salts of alkylbenzene sulfonic acids having 6 to 18 carbon atoms, such as sulfonic acid; alkyl naphthalenes having 2 to 18 carbon atoms, such as dimethylnaphthylsulfonic acid, diisopropylnaphthylsulfonic acid, dibutylnaphthylsulfonic acid, etc. Examples include alkali metal salts of sulfonic acids; alkali metal salts such as fluorinated sulfonic acids such as trifluoromethanesulfonic acid, and the like. These may be used alone or in combination of two or more. The component (D) can be used in the range of preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass with respect to the component (B) of the present invention.

  In the antistatic resin composition of the present invention, the amount of the component (B) used is 3 to 30% by mass, preferably 5 to 25 when the total of the component (A) and the component (B) is 100% by mass. It is used in the range of mass%, more preferably 5-23 mass%, particularly preferably 6-22 mass%. If it is less than 3% by mass, the antistatic property is inferior, and if it exceeds 30% by mass, the impact resistance and the appearance of the molded product are inferior.

Ingredient (C)
Component (C) of the present invention is at least one selected from the group consisting of a salt (C1) having an anion having a fluorinated alkylsulfonyl group and a nonionic surfactant (C2). By blending, the antistatic property can be further improved.
The component (C1) used here means a salt composed of an anion having one or more fluorinated alkylsulfonyl groups and an appropriate cation. Examples of the fluorinated alkylsulfonyl group contained in the anion include a fluorinated lower alkylsulfonyl group such as trifluoromethanesulfonic acid and pentafluoroethanesulfonic acid, particularly a perfluoroalkylsulfonyl group. The anion constituting the component (C1) includes, in addition to trifluoromethanesulfonic acid itself, one or more preferably a plurality of trifluoromethanesulfonyl groups such as bis (trifluoromethanesulfonyl) imide, tris (trifluoromethanesulfonyl) methide, and a hydrogen atom. Derivatives such as methide and ammonia substituted with. Typical examples of the cation constituting the component (C1) include alkali metals such as lithium, sodium and potassium. Specific examples of the component (C1) include lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide, potassium bis (trifluoromethanesulfonyl) imide, sodium bis (trifluoromethanesulfonyl) imide, and lithium tris (trifluoromethanesulfonyl) methide. , Potassium tris (trifluoromethanesulfonyl) methide, sodium tris (trifluoromethanesulfonyl) methide and the like. These can be used individually by 1 type or in combination of 2 or more types. Preferred components (C1) are bis (trifluoromethanesulfonyl) imidolithium and tris (trifluoromethanesulfonyl) methidelithium.

The component (C1) can be used as it is, can be used as a solution, or can be used in combination with a polymer having an ether bond in advance.
A particularly preferable solvent for dissolving the component (C1) is water or a compound represented by the following formula (8).

[In general formula (8), X is an alkylene group having 2 to 8 carbon atoms, a divalent hydrocarbon group containing an aromatic group, or a divalent alicyclic hydrocarbon group, and R is the same or different. 1 to 9 linear or branched alkyl groups, A is the same or different and represents an alkylene group having 2 to 4 carbon atoms, and n is the same or different and is an integer of 1 to 7. ]

What is preferable as a compound represented by the said General formula (8) is a thing in which R is an alkyl group which does not have a hydroxyl group at the terminal. Particularly preferred is bis [2- (2butoxyethoxy) ethyl] adipate (dibutoxyethoxyethyl adipate) or bis (2-butoxyethyl) phthalate.
The concentration in the case of dissolving the component (C1) of the present invention is preferably in the range of 0.1 to 80% by mass, more preferably 1 to 60% by mass.

  Examples of the polymer having an ether bond include polyethylene glycol, polyethylene oxide, polyethylene glycol, polyethylene oxide and the like modified with a functional group such as an epoxy group, a block copolymer composed of a polyolefin block and polyethylene glycol, and There exists the component (B) etc. of this invention.

  The solution of the component (C1) of the present invention is Sanko Chemical 0862-20R, 0862-13T, 0862-10T, AQ-50T (trade name), etc. manufactured by Sanko Chemical Co., Ltd. It can be obtained as Sanconol TBX-25 (trade name) manufactured by the company.

Examples of the nonionic surfactant of the component (C2) of the present invention include a polyhydric alcohol ester compound (C2-1), a nitrogen-containing compound (C2-2) and the like. They can be used in combination.
Examples of the polyhydric alcohol ester compound (C2-1) include glycerol such as glycerol monostearate, glycerol monomyristate, glycerol monopalmitate, glycerol monostearate, glycerol monobehenate, glycerol monooleate, and glycerol monolaurate. Diglycerin fatty acid esters such as fatty acid esters, diglycerin monomyristate, diglycerin monopalmitate, diglycerin monostearate, diglycerin monobehenate, diglycerin monooleate and the like, polyglycerin fatty acid esters, sorbitan monolaurate, sorbitan monobe Examples include sorbitan fatty acid esters such as henate and sorbitan monolaurate, and these can be used alone or in combination of two or more.
Particularly preferred are glycerin monolaurate, diglycerin monolaurate, sorbitan monostearate and those containing at least 20% by mass of these.

  Examples of the nitrogen-containing compound (C2-2) include lauryl diethanolamine, myristyl diethanolamine, palmityl diethanolamine, stearyl diethanolamine, oleyl diethanolamine, lauryl diisopropanolamine, myristyl diisopropanolamine, palmityl isopropanolamine, stearyl diisopropanolamine, oleyl diisopropanol. Amines, amines such as N, N-bishydroxyethylalkyl (alkyl group having 12 to 22 carbon atoms) amine, or lauryl diethanolamide, myristyl diethanolamide, palmityl diethanolamide, behenyl diethanolamide, oleyl diethanolamide, lauryl di Isopropanolamide, myristyl diisopropanolamide, PAL Chill diisopropanolamine amide, stearyl diisopropanol amide, there are amides such as oleyl monoisopropanolamide. These can be used alone or in combination of two or more. Preferred are the above amines, and more preferred are those containing 20% by mass or more of amino alcohols substituted with higher saturated hydrocarbon groups such as lauryldiethanolamine and stearyldiethanolamine. Moreover, a known additive can be blended with the above-mentioned compound for the purpose of improving antistatic properties. Examples thereof include higher alcohols having 12 to 18 carbon atoms, lubricants, silica, calcium silicate and the like. Further, for the purpose of improving miscibility, a master batch can be used. The component (C) of the present invention is preferably the above (C1), more preferably a combination of (C1) and (C2).

  The component (C) of the present invention is 0.01 to 10 parts by weight, preferably 0.1 to 8 parts by weight, more preferably 0 with respect to 100 parts by weight of the total of the components (A) and (B) of the present invention. 0.1 to 5 parts by mass, particularly preferably 0.5 to 5 parts by mass. If it is less than 0.01 part by mass, the effect of improving antistatic properties does not appear, and if it exceeds 10 parts by mass, the impact resistance and the appearance of the molded product are inferior.

  The antistatic resin composition of the present invention includes known weather resistance (light) agents, antioxidants, thermal stabilizers, lubricants, silicone oils, surfactants, plasticizers, sliding agents, colorants, dyes, foams. An agent, a processing aid (ultra high molecular weight acrylic polymer, ultra high molecular weight styrene polymer), flame retardant, crystal nucleating agent, and the like can be appropriately blended.

Moreover, a well-known inorganic and organic filler can be mix | blended with the antistatic resin composition of this invention. The filler used here is glass fiber, glass flake, glass fiber milled fiber, glass bead, hollow glass bead, carbon fiber, carbon fiber milled fiber, silver, copper, brass, iron powder or the like 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, hectorite, zinc oxide whisker, potassium titanate There are whisker, aluminum borate whisker, plate-like alumina, plate-like silica, and organically treated smectite, aramid fiber, phenol fiber, polyester fiber, etc., and these should be used alone or in combination of two or more. Can do.
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 inorganic / organic filler is usually used in the range of 1 to 200 parts by mass with respect to 100 parts by mass of the antistatic resin composition of the present invention.

  Further, the antistatic resin composition of the present invention includes other known polymers such as polyamide resin, polyamide elastomer, polybutylene terephthalate, polyethylene terephthalate, polyarylate, liquid crystal polyester, and other thermoplastic polyester resins, polyester elastomers, PMMA, methyl methacrylate / maleimide compound copolymer, polyphenylene ether, polyphenylene sulfide, aromatic polycarbonate, thermoplastic polyurethane, epoxy resin, phenol resin, urea resin, phenoxy resin and the like can be appropriately blended.

  The antistatic resin composition of the present invention can be obtained by melt-kneading the above-described constituent components with various extruders, Banbury mixers, kneaders, continuous kneaders, rolls, and the like. At the time of kneading, the above components of the present invention may be added together and kneaded, or may be added separately and kneaded. The antistatic resin composition of the present invention thus prepared includes injection molding, press molding, calender molding, T-die extrusion molding, inflation molding, lamination molding, vacuum molding, profile extrusion molding, and combinations thereof. A molded product can be obtained by a known molding method such as a molding method.

The thickness when processing the antistatic resin composition of the present invention into a sheet or film is preferably in the range of 10 μm to 100 mm.
The sheet and film may be a single layer sheet or film, may be multilayered with other materials, or may be a sheet or film laminated with an adhesive or the like. Furthermore, a known gas barrier film can be formed on the sheet or film.

When a multilayer sheet or a multilayer film is molded using the antistatic resin composition of the present invention, a sheet or film made of the antistatic resin composition of the present invention is laminated on one side of a sheet or film made of another material. A layer sheet or a two-layer film, or a three-layer sheet or a three-layer film obtained by laminating a sheet or a film made of the antistatic resin composition of the present invention on both surfaces of another layer as an intermediate layer can be used. As other materials used here, known polymers can be used, and the component (A) of the present invention is preferably used for them. Further, for the purpose of improving the rigidity and heat resistance, those containing the inorganic and organic fillers can be used.
The thickness of the antistatic resin composition of the present invention laminated on the two-layered and multilayered sheets and films is preferably 10 μm or more, more preferably 50 μm or more, particularly preferably for the purpose of stably developing antistatic properties. The thickness is 80 μm or more. As a method for obtaining such a multilayer sheet and film, a particularly preferable method is coextrusion by T-die and coextrusion by inflation. The sheet and film thus obtained can be formed into a molded product such as a tray by vacuum forming or the like as necessary.

  The molded products thus obtained include cases such as relay cases, wafer cases, reticle cases, and ask cases, trays such as liquid crystal trays, chip trays, memory trays, CCD trays, IC trays, IC carriers, etc. It can be used in the fields of carriers, protective sheets for film cutting, sheets such as sheets in a clean room, and vending machine internal members.

  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. In addition, various measurements in Examples and Comparative Examples were performed according to the following methods.

[1] Evaluation method (1) Gel content of rubbery polymer: According to the above method.
(2) Number average particle diameter of rubbery polymer latex;
The number average particle size of the rubbery polymer latex used for forming the component (A1) 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. The particle diameter of the dispersion-grafted rubber polymer particles in the component (A1) was confirmed by an electron microscope to be almost the same as the latex particle diameter. (3) Graft ratio of component (A1): According to the method described above.
(4) Acetone-soluble component of component (A1) and intrinsic viscosity [η] of component (A2);

(5) Antistatic property: damping characteristic A flat plate having a thickness of 2.4 mm or a sheet having a thickness of 1 mm is allowed to stand for 48 hours under conditions of a temperature of 23 ° C. and a humidity of 12% RH in accordance with US Federal Government Test Standard 101C 4046. After that, the time (seconds) from application of +5 KV to grounding and attenuation to 50 V was measured. The shorter the decay time, the better the antistatic property.
(6) Impact resistance;
The energy (kgf · cm) at which a striking rod having a diameter of 1/2 inch breaks a flat plate having a thickness of 2.4 mm or a sheet having a thickness of 1 mm at a speed of 2.4 m / sec was measured.
(7) Molded product appearance The thickness of a 2.4 mm flat plate or the surface of a 1 mm thick sheet was visually observed and visually evaluated according to the following evaluation criteria.
◯: Good with a smooth appearance.
X: Unevenness is seen on the surface and it is not smooth.
(8) Haze was measured according to ASTM D1003 for a transparent thickness 2.4 mm flat plate or a sheet having a thickness of 1 mm, and evaluated according to the following criteria.
A: Excellent in transparency (haze is 30% or less).
X: Transparency is inferior or opaque (haze exceeds 30%).

[2] Antistatic resin composition component (1) Component (A)
(1-1) Production Example 1; A1-1 (polybutadiene-styrene-acrylonitrile copolymer)
In a 7 L glass flask equipped with a stirrer, 75 parts of ion-exchanged water, 0.5 part of potassium rosinate, 0.1 part of tert-dodecyl mercaptan, polybutadiene latex (average particle size: 3500 kg, gel) in a nitrogen stream Content: 85%) 40 parts (solid content), 15 parts of styrene, and 5 parts of acrylonitrile were added, and the temperature was increased while 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 were added 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 latex of the reaction product was coagulated with an aqueous sulfuric acid solution, washed with water, and dried to obtain a rubber-reinforced styrene resin A1-1. The graft ratio of this polymer A1-1 was 68%, and the intrinsic viscosity [η] of the acetone-soluble component was 0.45 dl / g.

(1-2) Production Example 2; A1-2 (polybutadiene-styrene-methyl methacrylate copolymer)
Polybutadiene latex (average particle size: 2500 kg, gel content: 80%) 20 parts (solid content), potassium rosinate 0.5 part, ion exchange in a 7 L glass flask equipped with a stirrer in a nitrogen stream 150 parts of water was added and stirring was started. After adding 14.7 parts of methyl methacrylate and 5.3 parts of styrene, the temperature was raised, and when the internal temperature reached 40 ° C., the aqueous sulfoxylate-based auxiliary initiator solution and cumene hydroperoxide 0.05 Part was added to initiate the polymerization reaction. One hour after the start of the polymerization, an emulsion liquid consisting of 44 parts of methyl methacrylate, 16 parts of styrene, 0.5 part of potassium rosinate, 25 parts of ion-exchanged water, 0.1 part of cumene hydroperoxide, and sulfoxylate system start The polymerization reaction was carried out while continuously adding an aqueous solution of the auxiliary agent over 4 hours, and then stirring was continued for 2 hours. Thereafter, the mixture was cooled to 50 ° C. to complete the polymerization reaction. The reaction product latex was coagulated with an aqueous sulfuric acid solution, washed with water, and then dried to obtain rubber-reinforced styrene resin A1-2. The graft ratio of this polymer A1-2 was 83%, and the intrinsic viscosity [η] was 0.65.

(1-3) Production Example 3; A2-1 (hydroxyl group-containing vinyl compound copolymer styrene-acrylonitrile copolymer)
In Production Example 1, potassium rosinate was changed to potassium dodecylbenzenesulfonate without using polybutadiene latex. The monomer component in the first stage was changed to styrene / acrylonitrile / 2-hydroxy-ethyl-methacrylate = 22.5 / 7.5 / 3.5 parts. Further, the continuously added component was changed to styrene / acrylonitrile / 2-hydroxy-ethyl-methacrylate = 44.7 / 14.9 / 6.9 parts. Polymerization was conducted in the same manner as in Production Example 1 except for the above changes. The reaction product latex was coagulated with an aqueous magnesium sulfate solution, washed with water, and then dried to obtain a styrene polymer A2-1. The intrinsic viscosity [η] of the present polymer A2-1 was 0.44.

(1-4) Production Example 4; A2-2 (styrene-acrylonitrile copolymer)
Two jacketed polymerization reaction vessels equipped with ribbon wings with an internal volume of 30 L were connected and purged with nitrogen, and then 75 parts of styrene, 25 parts of acrylonitrile and 20 parts of toluene were continuously added to the first reaction vessel. A solution of 0.06 part of tert-dodecyl mercaptan and 5 parts of toluene as a molecular weight regulator, and 0.1 part of 1,1′-azobis (cyclohexane-1-carbonitrile) as a polymerization initiator and a solution of 5 parts of toluene 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. The polymerization temperature of the second reaction vessel supplied to the reaction vessel was 130 ° C., and the polymerization conversion was 75%. The copolymer solution obtained in the second reaction vessel was devolatilized directly from the unreacted monomer and solvent using a twin-screw, three-stage vented extruder, and the intrinsic viscosity
A styrene resin A2-2 having [η] 0.62 was obtained.

(1-5) Production Example 5; A2-3 (styrene-methyl methacrylate copolymer)
After substituting the stirrer and jacketed autoclave with nitrogen, 73.4 parts of methyl methacrylate, 26.6 parts of styrene, 20 parts of toluene, and 0.05 parts of tert-dodecyl mercaptan were charged in a nitrogen stream, followed by stirring and heating. Started. When the internal temperature reached 50 ° C., 0.5 part of benzoyl peroxide was added, the temperature was further increased, and after reaching 80 ° C., the polymerization reaction was carried out while controlling at a constant 80 ° C. 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. After cooling to 100 ° C., the reaction mixture was extracted from the autoclave, unreacted substances were distilled off by steam distillation, pulverized, devolatilized with a vented extruder, and pelletized to obtain a styrene polymer A2-3. The intrinsic viscosity [η] of the present polymer A2-3 was 0.65.

(2) Component (B)
(2-1); Polymer B1: Polyamide-polyether multi-block copolymer “Pelestat M-140” (trade name) manufactured by Sanyo Chemical Industries, Ltd. was used.
(2-2); Polymer B2: A polyamide-polyether multiblock copolymer “Pelestat NC6321” (trade name) manufactured by Sanyo Chemical Industries, Ltd. was used.
(2-3); Polymer B3: A polyamide-polyether multi-block copolymer “Pelestat 6500” (trade name) manufactured by Sanyo Chemical Industries, Ltd. was used.
(2-4); Polymer B4: Polyester-polyether multiblock copolymer “TEP004” (trade name) manufactured by Takemoto Yushi Co., Ltd. was used.

(3) Component (C)
(3-1); C1-1; Sankonol AQ-50T manufactured by Sanko Chemical Co., Ltd. (aqueous solution containing 50% of tris (trifluoromethanesulfonyl) methide lithium using water as a solvent)
(3-2); C1-2; Sankonol 0862-10T manufactured by Sanko Chemical Co., Ltd. (a solution having a tris (trifluoromethanesulfonyl) methide lithium content of 10% using an organic solvent as a solvent)
(3-3); C2-1; Kao's Electro Stripper TS-5 (nonionic surfactant; stearyl monoglyceride)

Examples 1-11, Comparative Examples 1-4
The components listed in Table 1 were mixed at a blending ratio shown in Table 1 using a Henschel mixer, and then melt-kneaded using a twin-screw extruder (cylinder setting temperature 220 ° C.) to be pelletized. The obtained pellets were sufficiently dried to obtain the antistatic resin composition of the present invention. The obtained composition was molded with an injection molding machine (220 ° C.) to obtain a flat plate having a thickness of 2.4 mm.
Further, by coextrusion (at a temperature of 200 ° C.), a layer having a thickness of 100 μm made of the antistatic resin composition was formed on the front and back surfaces of a core layer having a thickness of 800 μm made of the polymer shown in Table 1. A three-layer sheet of 0.0 mm was obtained.
The antistatic property, impact resistance, appearance of the molded product, and transparency were evaluated by the above methods using a flat plate having a thickness of 2.4 mm and a sheet having a thickness of 1.0 mm.

From the results described in Table 1, the following is clear.
The molded products of Examples 1 to 11 of the present invention are excellent in antistatic impact resistance and molded product appearance.
On the other hand, Comparative Example 1 is an example in which the amount of the component (B) of the present invention is small outside the scope of the invention and the amount of the component (A) of the present invention is large outside the scope of the present invention. Is inferior. Comparative Example 2 is an example in which the amount of the component (B) of the present invention is large outside the scope of the invention and the amount of the component (A) of the present invention is small in the scope of the present invention. Is inferior. Comparative Example 3 is an example in which the amount of the component (C) used in the present invention is small outside the scope of the invention, and the antistatic property is inferior. Comparative Example 4 is an example in which the amount of the component (C) used in the present invention is large outside the scope of the invention, and the impact resistance and the appearance of the molded product are inferior.

Since the antistatic resin composition of the present invention is a thermoplastic resin composition that combines excellent antistatic properties, impact resistance, and appearance of a molded product that has not been obtained in the past, a high performance is required. It can be used as a molding material for various parts in the electrical / electronic field, OA / home appliance field, sanitary field, etc.

Claims (6)

(A) Presence of rubbery polymer (a) comprising at least one selected from the group consisting of diene rubber, ethylene / α-olefin rubber, acrylic rubber, silicone rubber and silicone / acrylic IPN rubber Below, rubber-reinforced styrene resin (A1) obtained by polymerizing vinyl monomer (b) containing an aromatic vinyl compound, and / or (co) weight of vinyl monomer (b) 70 to 97% by mass of a styrenic resin composed of a coalescence (A2),
(B) selected from the group consisting of polyamide and / or polyester block (B1) , polyether (B2-a), polyether-containing hydrophilic polymer (B2-b) and anionic polymer (B2-c) A block copolymer having at least one hydrophilic polymer block (B2) of 5 to 30% by mass,
It contains the component (A) and the component (B) (however, the total of the component (A) and the component (B) is 100% by mass),
Further, the group consisting of (C) a salt (C1) having an anion having a fluorinated alkylsulfonyl group and a nonionic surfactant (C2) with respect to a total of 100 parts by mass of the component (A) and the component (B). Ri Na contain 0.01 to 10 parts by weight of at least one element more selected,
The vinyl monomer (b) of the styrene resin (A) further contains a vinyl cyanide compound, and is a group consisting of an acid anhydride group, a hydroxyl group, an amino group, an epoxy group, a carboxyl group, and an oxazoline group. A vinyl compound containing at least one functional group selected from the above (hereinafter referred to as “specific functional group-containing vinyl compound”), wherein the specific functional group-containing vinyl compound is a vinyl monomer (b). overall antistatic resin composition characterized that you have constitute 0.1 to 20 mass% of (100 wt%). The antistatic resin composition according to claim 1, wherein the specific functional group-containing vinyl compound is a vinyl compound containing a hydroxyl group. Component (C1) is at least one selected from the group consisting of bis (trifluoromethanesulfonyl) imidolithium and tris (trifluoromethanesulfonyl) methidelithium, and component (C2) is a polyhydric alcohol ester compound. The antistatic resin composition according to claim 1 or 2, characterized in that The component (C1) is 1 to 99% by mass and the component (C2) is 99 to 1% by mass (provided that the total of the component (C1) and the component (C2) is 100% by mass). 4. The antistatic resin composition according to any one of 1 to 3 . A molded article comprising the antistatic resin composition according to any one of claims 1 to 4 . The laminated body formed by laminating | stacking the sheet | seat or film which consists of an antistatic resin composition of any one of Claims 1-4 on the surface of at least one of the sheet | seat or film which consists of a styrene resin.