JP2007039670A - Resin composition for drawing processing and molded product given by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for drawing processing, capable of being molded into such a molded product that a part thereof molded at a high draw ratio has an expected antistatic performance, when the product is produced by the drawing processing, and to provide the molded product. <P>SOLUTION: This resin composition for the drawing processing contains [A] a styrene-based rubber-reinforced resin in an amount of 70-99 mass% and [B] a polymer-type antistatic agent in an amount of 30-1 mass%, wherein the styrene-based rubber-reinforced resin [A] comprises a rubber-reinforced resin (A1) which is obtained by polymerizing a vinyl-based monomer (b) containing an aromatic vinyl compound and at least one kind of compound selected from a vinyl cyanide compound, a (meth)acrylic acid ester compound, and a maleimide-based compound in the presence of a rubbery polymer (a), or comprises a mixture of the resin (A1) and a copolymer (A2) of the monomer (b). A film, etc., is formed by using the composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a resin composition for drawing and a molded body using the same. More specifically, the present invention relates to a resin composition for stretch processing and a molded body, which can be formed into a molded body having a desired antistatic performance at a site formed at a high stretch ratio when manufactured by stretching.

Styrenic resins such as ABS resins are excellent in molding processability, and are widely used for many applications without selecting the shape of the molded body. In recent years, molded articles having a predetermined draw ratio have been disclosed (for example, Patent Documents 1 and 2).
Conventionally, a thin-walled body such as a film, a molded product in which a curved portion of a container or the like becomes a thin-walled portion, and the like are manufactured by stretching, vacuum forming, or the like. However, when the molding material contains a functional additive such as an antistatic agent, the intended function may be reduced in the thin portion.

JP-A-7-323474 JP 2004-90415 A

  The present invention provides a resin composition for stretch processing and a molded body in which a part formed at a high stretch ratio can be a molded body having an expected antistatic performance when manufactured by stretching. Objective.

The present invention is shown below.
1. [A] A vinyl type containing an aromatic vinyl compound and at least one compound selected from a vinyl cyanide compound, a (meth) acrylic ester compound and a maleimide compound in the presence of the rubbery polymer (a). A rubber-reinforced copolymer resin (A1) obtained by polymerizing the monomer (b), or a copolymer (A2) of the rubber-reinforced copolymer resin (A1) and the vinyl monomer (b). And 70 to 99% by mass of [B] polymer type antistatic agent (provided that [A] + [B] = 100% by mass). A resin composition for drawing processing, comprising:
2. 2. The resin composition for stretching processing according to 1 above, wherein the polymer antistatic agent [B] is a polyamide-based elastomer and / or a polyether ester-based elastomer.
3. 3. The resin composition for stretching processing according to 1 or 2 above, wherein the cloudiness of a thin-walled body having a thickness of 0.03 to 0.1 mm is 10% or less.
4). The above 1 to 3 wherein the absolute value of the difference between the refractive index at 25 ° C. of the styrene rubber-reinforced resin [A] and the refractive index at 25 ° C. of the polymer antistatic agent [B] is 0.01 or less. The resin composition for drawing processing according to any one of the above.
5. 5. The resin composition for stretching processing according to any one of 1 to 4 above, comprising a thin part having a draw ratio of 1.5 to 20 times at least at one place, and the surface specific resistance of the thin part being 1 × A molded product characterized by being 10 ¹¹ Ω or less.
6). 6. The molded body according to 5 above, wherein the thin portion is formed by a method selected from calendar molding, inflation molding and vacuum molding.
7). 7. The molded product according to 5 or 6 above, wherein the molded product is selected from a film, a sheet, and a container.
8). 8. The molded article according to 7 above, which is used for electronic parts or electronic devices.

According to the resin composition for stretch processing of the present invention, a molded article having excellent stretch processability and sufficiently having predetermined antistatic performance can be easily obtained. In particular, the desired antistatic performance can be obtained even in a molded body having a part having a draw ratio of 1.5 times or more.
When the polymer antistatic agent [B] is a polyamide-based elastomer and / or a polyether ester-based elastomer, the surface specific resistance in the thin portion formed by stretching is 1 × 10 ¹¹ Ω or less. Thus, a molded article excellent in antistatic performance can be easily obtained.
According to the molded article of the present invention, the surface appearance does not deteriorate even when the draw ratio is high, the antistatic performance is excellent, and the wear resistance and dimensional stability are also excellent. Furthermore, when the absolute value of the difference between the refractive index of the styrene rubber-reinforced resin [A] and the refractive index of the polymer antistatic agent [B] is 0.01 or less, the molded article of the present invention Is excellent in transparency.

  The molded body of the present invention has excellent antistatic performance on the surface and is suitable for films, sheets, containers and the like. Therefore, it is useful as a packaging body for electronic parts, electronic devices, etc., a container (tray, etc.), a protective member, a partition; an underlay used when cutting various members, etc .; a clean room structural member (wall, curtain, etc.) It is.

Hereinafter, the present invention will be described in detail.
1. Stretching Resin Composition The stretchable resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) is composed of 70 to 99 mass% of component [A] and 30 to 1 mass of component [B]. % (However, [A] + [B] = 100 mass%).
In this specification, “(co) polymerization” means homopolymerization and copolymerization, “(meth) acryl” means acryl and methacryl, “(meth) acrylate” means acrylate and methacrylate. means.

1-1. Ingredient [A]
Component [A], that is, styrene rubber-reinforced resin [A] is an aromatic vinyl compound, a vinyl cyanide compound, a (meth) acrylic acid ester compound, and a maleimide resin in the presence of rubbery polymer (a). A rubber-reinforced copolymer resin (A1) obtained by polymerizing a vinyl monomer (b) containing at least one compound selected from compounds, or the rubber-reinforced copolymer resin (A1) and the vinyl It is a styrene rubber-reinforced resin comprising a mixture of the copolymer (A2) of the monomer (b) (hereinafter also referred to as “mixture (A3)”).

  The rubbery polymer (a) may be a homopolymer or a copolymer. Specific examples include diene polymers and non-diene polymers. These may be used alone or in combination.

Diene polymers include homopolymers such as polybutadiene and polyisoprene; styrene / butadiene copolymers such as styrene / butadiene copolymers, styrene / butadiene / styrene copolymers, and acrylonitrile / styrene / butadiene copolymers. Styrene / isoprene copolymers, styrene / isoprene / styrene copolymers, styrene / isoprene copolymers such as acrylonitrile / styrene / isoprene copolymers; hydrides of the above (co) polymers, and the like.
Examples of non-diene polymers include polyolefin homopolymers; ethylene / α-olefin copolymers such as ethylene / propylene copolymers and ethylene / butene-1 copolymers; ethylene / propylene / 5-ethylidene-2-norbornene. Copolymers, ethylene / α-olefin / non-conjugated diene copolymers such as ethylene / butene-1 / 5-ethylidene-2-norbornene copolymer; urethane rubbers; acrylic rubbers; silicone rubbers; silicone acrylics Examples include IPN rubber.
Of these, diene polymers are preferred, and polybutadiene, styrene / butadiene copolymers and the like are particularly preferred.
Each (co) polymer may be a block (co) polymer or a random (co) polymer. Furthermore, it may be a non-crosslinked polymer or a crosslinked polymer.
When a diene polymer and an acrylic rubber are used as the rubber polymer (a), a transparent or transparent component [A] is easily obtained.

  The rubbery polymer (a) is preferably in the form of particles, and the weight average particle diameter of the rubbery polymer (a) when the latex is produced is preferably 100 to 800 nm, more preferably. Is 200 to 400 nm, particularly preferably 200 to 350 nm. If the weight average particle diameter is less than 100 nm, the impact resistance of the molded product tends to be reduced, and if it exceeds 800 nm, the appearance of the molded product tends to be reduced. The weight average particle diameter can be measured by a laser diffraction method, a light scattering method, or the like.

  The rubbery polymer (a) is, for example, JP-A-61-233010, JP-A-59-93701, JP-A-56-56 as long as the weight average particle diameter is within the above range. What was enlarged by well-known methods, such as the method described in 167704 gazette etc., can also be used.

  As a method for producing the rubbery polymer (a), emulsion polymerization is preferable in consideration of adjustment of the average particle diameter and the like. In this case, the average particle size can be adjusted by selecting the production conditions such as the type of emulsifier and the amount used, the type and amount of initiator used, the polymerization time, the polymerization temperature, and the stirring conditions. Another method for adjusting the average particle size (particle size distribution) may be a method of blending two or more kinds of rubbery polymers (a) having different particle sizes.

  The vinyl monomer (b) used for forming the rubber-reinforced copolymer resin (A1) includes an aromatic vinyl compound, and otherwise, a vinyl cyanide compound, a (meth) acrylic acid ester compound and a maleimide. Each of these compounds can be used alone or in combination of two or more.

  As the aromatic vinyl compound, any compound having at least one vinyl bond and at least one aromatic ring can be used without any particular limitation. Examples thereof include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, vinyl toluene, β-methyl styrene, ethyl styrene, p-tert-butyl styrene, vinyl xylene, vinyl naphthalene, monochlorostyrene, dichloromethane. Examples thereof include styrene, monobromostyrene, dibromostyrene, and fluorostyrene. Of these, styrene and α-methylstyrene are preferred. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Of these, acrylonitrile is preferred. Moreover, these can be used individually by 1 type or in combination of 2 or more types.
Examples of (meth) acrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, methyl acrylate, acrylic acid Examples include ethyl, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and the like. Of these, methyl methacrylate is preferred. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

  Examples of maleimide compounds include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N-cyclohexylmaleimide and the like. It is done. These can be used alone or in combination of two or more. In addition, as another method for introducing a unit composed of a maleimide compound, for example, a method in which maleic anhydride is copolymerized and then imidized may be used.

In addition to the above compounds, an acid anhydride; a vinyl compound having a functional group such as a hydroxyl group, an amino group, an epoxy group, an amide group, a carboxyl group, or an oxazoline group can be used as necessary.
Examples of the acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These can be used alone or in combination of two or more.
Examples of the vinyl compound having a functional group include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, hydroxystyrene, N, N-dimethylaminomethyl methacrylate, N, N-dimethylaminomethyl acrylate, N, N -Diethyl-p-aminomethylstyrene, glycidyl methacrylate, glycidyl acrylate, 3,4-oxycyclohexyl methacrylate, 3,4-oxycyclohexyl acrylate, vinyl glycidyl ether, methallyl glycidyl ether, allyl glycidyl ether, methacrylamide Acrylamide, methacrylic acid, acrylic acid, vinyl oxazoline and the like. These can be used alone or in combination of two or more.

  The vinyl monomer (b) contains an aromatic vinyl compound. In this case, the polymerization rate (b1) / () of the aromatic vinyl compound (b1) and the other vinyl compound (b2). b2) is preferably (10 to 90)% by mass / (90 to 10)% by mass, more preferably (15 to 80)% by mass / (85 to 20)% by mass, when the total of these is 100% by mass. %. If the amount of the aromatic vinyl compound (b1) used is too small, the moldability tends to be inferior. On the other hand, when there is too much usage-amount of this compound, the chemical resistance of the composition of this invention and a molded article containing the same, heat resistance, etc. may not be enough.

The vinyl monomer (b) used for forming the rubber-reinforced copolymer resin (A1) is preferably used in the following combinations.
(1) An aromatic vinyl compound and a vinyl cyanide compound.
(2) Aromatic vinyl compounds, vinyl cyanide compounds and (meth) acrylic acid ester compounds.
(3) Aromatic vinyl compounds and (meth) acrylic acid ester compounds.
Among the above, in the case of (2) and (3), a transparent or transparent component [A] is easily obtained.

  The rubber-reinforced copolymer resin (A1) is obtained by polymerizing the vinyl monomer (b) in the presence of the rubber polymer (a). The rubber-reinforced copolymer resin (A1) may be one or more of rubber-reinforced copolymer resins (i) obtained using the monomer (1) as the vinyl monomer (b). And may be one or more of the rubber-reinforced copolymer resins (ii) obtained by using the monomer (2) as the vinyl monomer (b), and the vinyl monomer (b) ) May be one or more of rubber-reinforced copolymer resins (iii) obtained using the monomer (3) above. Furthermore, two or more of these (i) to (iii) may be appropriately combined.

  As described above, the component [A] may be only the rubber-reinforced copolymer resin (A1), and is obtained by polymerizing the rubber-reinforced copolymer resin (A1) and the vinyl monomer (b). It may be a mixture (A3) with the copolymer (A2) obtained in this way. As the vinyl monomer (b), the monomer compound used for forming the rubber-reinforced copolymer resin (A1) can be used. Therefore, the copolymer (A2) is a copolymer obtained by polymerizing a monomer compound having exactly the same composition as the vinyl monomer (b) used for forming the rubber-reinforced copolymer resin (A1). It may be a copolymer, may be a copolymer obtained by polymerizing the same type of monomer compound with different compositions, and may further polymerize different types of monomer compounds with different compositions. It may be a copolymer obtained. Two or more of these copolymers may be contained.

Examples of the copolymer (A2) include the following (4) to (9). In addition, the compound used for formation of the said rubber | gum reinforcement | strengthening copolymer resin (A1) can be applied to each monomer, and a preferable compound is also the same. Moreover, the content rate of each monomer unit which comprises a copolymer (A2) is not specifically limited.
(4) One or more types of copolymers obtained by polymerizing an aromatic vinyl compound and a vinyl cyanide compound.
(5) One or more kinds of copolymers obtained by polymerizing an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acrylic acid ester compound.
(6) One or more kinds of copolymers obtained by polymerizing an aromatic vinyl compound and a (meth) acrylic acid ester compound.
(7) One or more types of copolymers obtained by polymerizing an aromatic vinyl compound and a maleimide compound.
(8) One or more types of copolymers obtained by polymerizing aromatic vinyl compounds, vinyl cyanide compounds and maleimide compounds.
(9) One or more kinds of copolymers obtained by polymerizing an aromatic vinyl compound, a (meth) acrylic acid ester compound and a maleimide compound.
These can be used alone or in combination of two or more.
Among the above, in the case of (5), (6) and (9), a transparent or transparent component [A] is easily obtained.

  Specific examples of the copolymer (A2) include acrylonitrile / styrene copolymer, acrylonitrile / α-methylstyrene copolymer, styrene / acrylonitrile / methyl methacrylate copolymer, styrene / methyl methacrylate copolymer, Examples include styrene / N-phenylmaleimide copolymers, styrene / acrylonitrile / N-phenylmaleimide copolymers, and styrene / methyl methacrylate / N-phenylmaleimide copolymers.

  In any case where the component [A] is the rubber-reinforced copolymer resin (A1) and the mixture (A3), the rubbery polymer contained in the resin composition for stretch processing of the present invention. Content of (a) becomes like this. Preferably it is 10-50 mass%, More preferably, it is 10-35 mass%. When the content of the rubbery polymer (a) is in this range, the molding processability and the rigidity are excellent.

Next, a method for producing the rubber-reinforced copolymer resin (A1) and the copolymer (A2) will be described.
The production method of the rubber-reinforced copolymer resin (A1) is not particularly limited, and a known polymerization method such as emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization and the like can be applied. Of these, emulsion polymerization is preferred.
In the production of the rubber-reinforced copolymer resin (A1), the rubber polymer (a) and the vinyl monomer (b) are present in the reaction system in the presence of the total amount of the rubber polymer (a). In addition, the vinyl-based monomer (b) may be added all at once, or divided or continuously. Moreover, the method which combined these may be used. Furthermore, you may superpose | polymerize by adding the whole quantity or one part of rubber-like polymer (a) in the middle of superposition | polymerization.
When producing 100 parts by mass of the rubber-reinforced copolymer resin (A1), the amount of the rubbery polymer (a) used is preferably 10 to 75 parts by mass, more preferably 10 to 55 parts by mass, and even more preferably 15 to 55 parts by mass.
Further, for each use amount of the rubber polymer (a) and the vinyl monomer (b), when the total of the rubber polymer (a) and the vinyl monomer (b) is 100 parts by mass, The amount of the vinyl monomer (b) used is preferably 25 to 90 parts by mass, more preferably 45 to 90 parts by mass, and still more preferably 45 to 85 parts by mass.

When the rubber-reinforced copolymer resin (A1) is produced by emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water and the like are used.
As a polymerization initiator, a redox system in which an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, etc. is combined with a reducing agent such as a sugar-containing pyrophosphate formulation or a sulfoxylate formulation. Initiators; persulfates such as potassium persulfate; peroxides such as benzoyl peroxide (BPO), lauroyl peroxide, tert-butyl peroxylaurate, and tert-butyl peroxymonocarbonate. These can be used alone or in combination of two or more. Furthermore, the polymerization initiator can be added to the reaction system all at once or continuously.
The usage-amount of the said polymerization initiator is 0.1-3 mass% normally with respect to the said vinylic monomer (b) whole quantity, Preferably it is 0.1-2 mass%.

Chain transfer agents include octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, mercaptans such as tert-tetradecyl mercaptan, terpinolene, α- Examples include methylstyrene dimer. These can be used alone or in combination of two or more.
The amount of the chain transfer agent used is usually 0.1 to 3% by mass with respect to the total amount of the vinyl monomer (b).

Emulsifiers include higher alcohol sulfates, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, aliphatic sulfonates such as sodium lauryl sulfate, higher aliphatic carboxylates, and anionic surfactants such as phosphates. And nonionic surfactants such as alkyl ester type and alkyl ether type of polyethylene glycol. These can be used alone or in combination of two or more.
The usage-amount of the said emulsifier is 0.5-3 mass% normally with respect to the said vinylic monomer (b) whole quantity.
In addition, the polymerization temperature in the case of emulsion polymerization is 30-95 degreeC normally, Preferably it is 40-90 degreeC.

The latex obtained by emulsion polymerization is usually purified by coagulating with a coagulant to make a resin powder, and then washing and drying the resin. Examples of the coagulant include inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride, and sodium chloride; inorganic acids such as sulfuric acid, hydrochloric acid, and acetic acid; organic acids such as acetic acid, lactic acid, citric acid, and malic acid.
In the case where a plurality of rubber-reinforced copolymer resins (A1) are used in combination, the resins may be isolated and then mixed, but as another method, after the latex containing each resin is manufactured, The mixed rubber-reinforced copolymer resin (A1) can be obtained by mixing and then solidifying.

When manufacturing the said rubber | gum reinforcement | strengthening copolymer resin (A1) by solution polymerization, block polymerization, or suspension polymerization, it can carry out by a conventional method.
In the case of solution polymerization, the vinyl monomer (b) is usually dissolved in an aromatic hydrocarbon such as toluene or ethylbenzene; ketones such as methyl ethyl ketone; an inert polymerization solvent such as acetonitrile, dimethylformamide, or N-methylpyrrolidone. The polymerization may be performed in the presence of a polymerization initiator, or may be performed in the absence of a polymerization initiator. In addition, the polymerization temperature in the case of solution polymerization is 100-150 degreeC normally, Preferably it is 100-130 degreeC.

The graft ratio of the rubber-reinforced copolymer resin (A1) is preferably 10 to 150%, more preferably 10 to 100%, and particularly preferably 20 to 100%. When the graft ratio of the rubber-reinforced copolymer resin (A1) is less than 10%, the surface appearance and impact resistance of the composition of the present invention and a molded article containing the composition may be lowered. On the other hand, if it exceeds 150%, the moldability is inferior.
Here, the graft ratio refers to x grams of the rubber component in 1 gram of the rubber-reinforced copolymer resin (A1), and 1 gram of the rubber-reinforced copolymer resin (A1) as acetone (however, the rubbery polymer (a)). Is an acrylic rubber, acetonitrile is used.) When the insoluble content when dissolved in y-gram is obtained, the value is obtained by the following formula.
Graft rate (%) = {(y−x) / x} × 100

In addition, the intrinsic viscosity [η] (methyl ethyl ketone) of a soluble component of acetone of the rubber-reinforced copolymer resin (A1) (provided that acetonitrile is used when the rubbery polymer (a) is an acrylic rubber). (Measured at 30 ° C.) is preferably 0.1 to 0.8 dl / g, more preferably 0.2 to 0.6 dl / g, and particularly preferably 0.2 to 0.5 dl / g. By setting it as this range, it is excellent in molding processability, and the impact resistance of the composition of this invention and a molded object containing the same is also excellent.
The above graft ratio and intrinsic viscosity [η] are the types and amounts of polymerization initiator, chain transfer agent, emulsifier, solvent, etc., and the polymerization time when the rubber-reinforced copolymer resin (A1) is produced. It can be easily controlled by selecting the polymerization temperature and the like.

  Further, the production method of the copolymer (A2) is not particularly limited, and the monomer component is subjected to solution polymerization using a polymerization initiator or the like applied to the production of the rubber-reinforced copolymer resin (A1). It can be produced by polymerization by bulk polymerization, emulsion polymerization, suspension polymerization or the like, or by thermal polymerization without using a polymerization initiator. These polymerization methods may be combined.

  The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the copolymer (A2) is preferably 0.1 to 0.8 dl / g, more preferably 0.2 to 0.8 dl / g. . When the intrinsic viscosity [η] is within the above range, the physical property balance between molding processability and impact resistance is excellent. Incidentally, the intrinsic viscosity [η] of the copolymer (A2) can be controlled by adjusting the production conditions as in the case of the rubber-reinforced copolymer resin (A1).

  The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the above-mentioned component [A] is soluble in acetone (however, when the rubbery polymer (a) is acrylic rubber, acetonitrile-soluble). , Preferably 0.1 to 0.8 dl / g, more preferably 0.2 to 0.8 dl / g. When the intrinsic viscosity [η] is within the above range, the physical property balance between molding processability and impact resistance is excellent.

  The refractive index of the component [A] at 25 ° C. depends on the type of the rubbery polymer (a) and is not particularly limited, but is preferably 1.500 to 1.518, more preferably 1.510 to 1. .518, more preferably 1.515 to 1.518. The refractive index can be measured with an Abbe refractometer.

The transparency of the molded article containing the composition of the present invention is determined by the type (configuration) of the component [A] and further by the types of the components [A] and [B]. In the case of forming a molded article having transparency or transparency, the rubber-reinforced copolymer resin (A1) has a refractive index of preferably 1.500 to 1.518, more preferably as the rubbery polymer (a). The refractive index when the polymer is 1.510 to 1.518, more preferably 1.515 to 1.518, and the vinyl monomer (b) is preferably 1.500 to 1. It is preferable to use a monomer having a viscosity of 1.518 to 1.518, more preferably 1.515 to 1.518. Thereby, the rubber-reinforced copolymer resin (A1) to be obtained has a refractive index in the above range. The absolute value of the difference between the refractive index of the rubbery polymer (a) and the refractive index of the polymer of the vinyl monomer (b) is preferably 0.008 or less, more preferably 0.005 or less. Especially preferably, it is 0.003 or less. The smaller this difference, the better the transparency.
The refractive index of the copolymer (A2) is preferably 1.500 to 1.518, more preferably 1.510 to 1.518, and still more preferably 1.515 to 1.518.
When the component [A] is a mixture (A3), the absolute value of the difference between the refractive index of the rubber-reinforced copolymer resin (A1) and the refractive index of the copolymer (A2) is preferably 0.00. 008 or less, more preferably 0.005 or less, particularly preferably 0.003 or less. The smaller this difference, the better the transparency.

  The refractive index of the component [A] is preferably 1.500 to 1.518, more preferably 1.510 to 1.518, and still more preferably 1.515 to 1.518, and the component [A] ] (Meth) acrylic acid ester (preferably methacrylic acid ester) in polymer components (polymer of vinyl monomer (b)) other than rubbery polymer (a). If the monomer unit amount is preferably 40% by mass or more, more preferably 50% by mass or more, transparency or transparency is easily obtained, and the generation amount of outgas is small, and electronic parts, electronic devices, etc. It is useful as a molding material for packaging and containers. The monomer unit amount can be measured by a known method.

1-2. Ingredient [B]
As the component [B], that is, the polymer type antistatic agent [B], conventionally known ones can be used. Specifically, polyamide elastomers (polyether amide, polyether ester amide, polyether) can be used. Polyetherester elastomers; polyester elastomers; polyalkylene oxide polymers such as polyethylene oxide / epichlorohydrin copolymers; polyalkylbenzene sulfonates; polyethylene glycol (meth) acrylate copolymers, methoxy Acrylic copolymers such as polyethylene glycol (meth) acrylate copolymer; quaternary ammonium base-containing (meth) acrylate copolymer, quaternary ammonium base-containing maleimide copolymer, quaternary ammonium base-containing methacryl Quaternary ammonium salt-based copolymer bromide copolymer; carbobetaingrafted copolymer betaine copolymers such as, waxes, ionomer resins. Of these, polyamide elastomers and polyether ester elastomers are preferred.

  Hereinafter, the polyamide elastomer and the polyether ester elastomer will be described.

(1) Polyamide-based elastomer A typical example of the polyamide-based elastomer is a block copolymer containing a hard segment (x1) composed of a polyamide component and a soft segment (x2) composed of a poly (alkylene oxide) glycol component. Etc.

  The polyamide component used for forming the hard segment (x1) is not particularly limited as long as it is a polymer having an acid amide bond (—CO—NH—) in the main chain. This polyamide component is usually produced by a known method such as ring-opening polymerization of a lactam compound having a ring structure, polymerization of aminocarboxylic acid, condensation polymerization of dicarboxylic acid and diamine compound. Accordingly, the polyamide component is used as a homopolyamide, a copolyamide or the like.

Examples of the lactam compound used in the ring-opening polymerization include ε-caprolactam and ω-laurolactam.
Examples of the aminocarboxylic acid include aminocaproic acid, aminoenanoic acid, aminocaprylic acid, aminobergonic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, and 12-aminododecanoic acid.

  The dicarboxylic acids used in the condensation polymerization of dicarboxylic acids and diamine compounds include adipic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid, 2-methylterephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid. An acid etc. are mentioned. Examples of the diamine compound include ethylene diamine, tetramethylene diamine, hexamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,3,4-trimethylhexamethylene diamine, 2,4,4. -Trimethylhexamethylenediamine, bis (p-aminocyclohexyl) methane, m-xylylenediamine, p-xylylenediamine, paraphenylenediamine, metaphenylenediamine and the like.

  Examples of the polyamide component include nylon 4, 6, 7, 8, 11, 12, 6.6, 6.9, 6.10, 6.11, 6.12, 6T, 6 / 6.6, and 6/12. 6 / 6T, 6T / 6I, and the like can be used. In addition, the terminal of this polyamide component may be sealed with carboxylic acid, amine or the like. Examples of the carboxylic acid include aliphatic monocarboxylic acids such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Examples of the amine include aliphatic primary amines such as hexylamine, octylamine, decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, and behenylamine.

  The number average molecular weight of the polyamide component is preferably 500 to 10,000, more preferably 500 to 5,000. In addition, when using 2 or more types of polyamide components, the measured value when mixed may be in the above range.

As the poly (alkylene oxide) glycol component used for forming the soft segment (x2), a known polymer such as a polymer represented by the following formula (I) is used singly or in combination of two or more. be able to.
HO (CH ₂ CH ₂ O) _m (CH ₂ CH (X) O) _n H (I)
[Wherein, X represents a hydrogen atom (—H) or a substituent —CH ₃ , —CH ₂ Cl, —CH ₂ Br, —CH ₂ I or —CH ₂ OCH ₃ , and n ≧ 0, m ≧ 0. And (n + m) ≧ 20. ]

Specific examples of the poly (alkylene oxide) glycol component include polyethylene glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene). Oxide) glycol, polyethylene oxide, polypropylene oxide, block or random copolymer of ethylene oxide and propylene oxide, block or random copolymer of ethylene oxide and tetrahydrofuran, alkylene oxide adduct of bisphenol A, and the like. Of these, an alkylene oxide adduct of polyethylene glycol and bisphenol A is preferred.
Note that both ends of the poly (alkylene oxide) glycol component may be aminated and / or carboxylated.

  The number average molecular weight of the poly (alkylene oxide) glycol component is preferably 200 to 20,000, more preferably 300 to 10,000, and still more preferably 300 to 4,000. In the case of using two or more kinds of poly (alkylene oxide) glycol components, the measured value when mixed may be within the above range. The number average molecular weight according to the present invention is measured by gel permeation chromatography (GPC).

The polyamide-based elastomer can be obtained by polymerizing a polyamide component and a poly (alkylene oxide) glycol component under reduced pressure or normal pressure.
The respective proportions of the polyamide component and the poly (alkylene oxide) glycol component are preferably 10 to 95% by mass and 90 to 5% by mass, more preferably 20 to 90% by mass, when the total of these components is 100% by mass. % And 80 to 10% by mass, particularly preferably 30 to 70% by mass and 70 to 30% by mass. If the proportion of the polyamide component used is less than 10% by mass, the resulting polyamide-based elastomer may not be sufficiently compatible with the component [A]. On the other hand, if it exceeds 95% by mass, the effect as an antistatic agent is exhibited. May not be.
In the polymerization, an antimony catalyst, a tin catalyst, a titanium catalyst, a zirconium catalyst, an acetate metal salt catalyst, or the like can be used.

In the polymerization of the polyamide component and the poly (alkylene oxide) glycol component, a dicarboxylic acid, a diamine compound or the like can be used in combination as a polymerization raw material.
Examples of the dicarboxylic acid include aromatic dicarboxylic acid, alicyclic dicarboxylic acid, and aliphatic dicarboxylic acid. Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 3 -Sodium sulfoisophthalate and the like. Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4-dicarboxylic acid, and the like. Examples of the aliphatic dicarboxylic acid include succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid and the like. Of these, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, adipic acid and dodecanedicarboxylic acid are preferred. Moreover, these dicarboxylic acids can be used individually by 1 type or in combination of 2 or more types.

  As the diamine compound, aromatic diamine compounds, alicyclic diamine compounds and aliphatic diamine compounds are used. Examples of the aromatic diamine compound include p-phenylenediamine, m-phenylenediamine, diaminodiphenyl ether, diaminodiphenylmethane, and the like. Examples of the alicyclic diamine compound include piperazine, diaminodicyclohexylmethane, cyclohexyldiamine, and the like. Examples of the aliphatic diamine compound include hexamethylene diamine, ethylene diamine, propylene diamine, and octamethylene diamine. Of these, hexamethylenediamine is preferred. Moreover, these diamine compounds can be used individually by 1 type or in combination of 2 or more types.

  Bonding of hard segment (x1) and soft segment (x2) is achieved by polymerization of polyamide component and poly (alkylene oxide) glycol component, or polymerization of polyamide component, poly (alkylene oxide) glycol component and dicarboxylic acid, diamine compound, etc. Depending on the terminal structure of the soft segment (x2), it is usually an ester bond or an amide bond.

  As the polyamide-based elastomer, (1) a polyamide obtained by polymerization of an aminocarboxylic acid having 6 or more carbon atoms or polymerization of a lactam compound, or a diamine compound and dicarboxylate having 6 or more carbon atoms is used. Obtained by using the obtained polyamide, (2) polyethylene glycol having a number average molecular weight of 200 to 20,000, and (3) dicarboxylic acid having 4 to 20 carbon atoms, wherein the polyether ester unit is the whole polymer. Polyether ester amides with respect to 10 to 95% by weight are preferred.

The reduced viscosity η _{sp / c} (measured using a 0.5 g / 100 ml formic acid solution at 25 ° C.) of the polyamide-based elastomer is preferably 0.5 to 3.0 dl / g, more preferably 1.0 to 2.5 dl / g. The polyamide elastomer may have a reduced molecular weight due to thermal deterioration during the production of the composition of the present invention or during molding, but the reduced viscosity η _{sp / c} in the final product is preferably 0.00. 3 dl / g or more.

(2) Polyether Ester Elastomer Typical examples of the polyether ester elastomer include a hard segment (y1) made of a polyester component and a soft segment (y2) made of a poly (alkylene oxide) glycol component. Block copolymers and the like.

  As a polyester component used for formation of a hard segment (y1), any of aliphatic polyester, alicyclic polyester, and aromatic polyester may be sufficient. This polyester component is usually produced by a reaction between an acid component containing a dicarboxylic acid and / or an ester-forming derivative of a dicarboxylic acid and a diol component containing a diol compound and / or an ester-forming derivative of a diol compound. Accordingly, the polyester component is used as a homopolyester, a copolyester or the like.

Among the acid components, dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4 ′. -Aromatic dicarboxylic acids such as diphenylmethane dicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, and 4,4′-diphenylisopropylidenedicarboxylic acid. These substitution products (alkyl group substitution products such as methyl isophthalic acid) and derivatives (alkyl ester compounds such as dimethyl terephthalate and dimethyl 2,6-naphthalenedicarboxylate) can also be used.
Furthermore, oxyacids and their ester-forming derivatives such as p-oxybenzoic acid and p-hydroxyethoxybenzoic acid can also be used.
The said acid component can be used individually by 1 type or in combination of 2 or more types.

Examples of the diol component include aliphatic glycols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and neopentyl glycol; and alicyclic glycols such as 1,4-cyclohexanedimethanol. In addition, these substitution bodies and derivatives can also be used. A cyclic ester compound such as ε-caprolactone can also be used.
Furthermore, long-chain diol compounds (polyethylene glycol, polytetramethylene glycol, etc.), alkylene oxide addition polymers of bisphenols, etc. (ethylene oxide addition polymers of bisphenol A, etc.), etc. can be used as necessary. .
The said diol component can be used individually by 1 type or in combination of 2 or more types.

  Examples of the polyester component include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane-1,4-dimethyl terephthalate, polyneopentyl terephthalate, polyethylene isophthalate, polyethylene naphthalate, polybutylene naphthalate, poly Hexamethylene naphthalate or the like can be used. Also, a copolyester can be used.

The average molecular weight of the polyester component is not particularly limited, but is preferably 0.3 to 2.5 dl / g, more preferably 0.5 to 2.5 dl / g, as a reduced viscosity η _{sp / c serving} as an index of the average molecular weight. g.

  As the poly (alkylene oxide) glycol component used for forming the soft segment (y2), the soft segment (x2) can be applied as it is.

  The polyether ester-based elastomer can be used alone as an antistatic agent, but by using a composition in combination with an organic sulfonic acid compound, a phenol compound, etc., it can impart excellent antistatic properties. it can.

The organic sulfonic acid compound is not particularly limited, and a compound formed from an organic sulfonic acid and a base is preferable.
Examples of the organic sulfonic acid compounds include alkyl sulfonates having 8 to 24 carbon atoms in the alkyl group, alkylbenzene sulfonates having 6 to 18 carbon atoms in the alkyl group, and alkyls having 2 to 18 carbon atoms in the alkyl group. Naphthalene sulfonate is preferred. Specific examples include tetradecyl sulfonate, dodecyl phenyl sulfonate, dimethyl naphthyl sulfonate, sodium tetradecyl sulfonate, sodium dodecyl phenyl sulfonate, sodium dimethyl naphthyl sulfonate, tetrabutyl dodecyl phenyl sulfonate. Examples thereof include phosphonium.
Some of the above compounds are used as surfactants, but these surfactants can be used as they are.
The said organic sulfonic acid type compound can be used individually by 1 type or in combination of 2 or more types.

Examples of the phenol-based compound is not particularly limited, and phenol skeleton (-C 6 H _{5 OH)} may be a compound comprising only one may be a compound containing two or more.
Examples of the phenol compound include 3,9-bis [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy) -1,1-dimethylethyl] -2,4. , 8,10-tetraoxaspiro (5,5) undecane (molecular weight 741), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) Examples include benzene (molecular weight 775), tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate (molecular weight 784), and the like. Of these, compounds having a molecular weight in the range of 700 to 1,200 are more preferred.
Although some of the above compounds are used as antioxidants, these antioxidants can be used as they are.
The said phenolic compound can be used individually by 1 type or in combination of 2 or more types.

  A preferred configuration of the antistatic agent containing the polyether ester elastomer, the organic sulfonic acid compound, and the phenol compound is as follows. That is, when the total of these three components is 100% by mass, the organic sulfonic acid compound is 4 to 30% by mass, preferably 10 to 30% by mass, and the phenolic compound is 0.1 to 3.5% by mass. The content is preferably 0.2 to 2% by mass, and the remainder is a polyether ester elastomer. By setting the content of each component within the above range, excellent antistatic performance can be imparted.

  Any one of the above-mentioned polyamide-based elastomer and polyether ester-based elastomer may be used alone as component [B], or may be used in combination.

  The above-mentioned polyamide-based elastomer and polyether ester-based elastomer include an alkali metal salt such as lithium, sodium and potassium; and a component [B] formed by blending a salt such as an alkaline earth metal salt such as magnesium and calcium. It can also be used. By containing these salts, the antistatic performance can be further improved. The salt may be blended before, during or after the production of the polyamide-based elastomer or the polyether ester-based elastomer, and further during the production of the present composition.

Examples of the salts include halides, inorganic acid salts, and organic acid salts.
Examples of the alkali metal halide include lithium chloride, sodium chloride, potassium chloride, lithium bromide, sodium bromide, and potassium bromide.
Examples of the alkaline earth metal halide include magnesium chloride and calcium chloride.
Examples of alkali metal inorganic acid salts include perchlorates such as lithium perchlorate, sodium perchlorate, and potassium perchlorate.

Organic acid salts include carboxylates of alkali metals such as potassium acetate and lithium stearate; octyl sulfonic acid, dodecyl sulfonic acid, tetradecyl sulfonic acid, stearyl sulfonic acid, tetracosyl sulfonic acid, 2-ethylhexyl sulfonic acid, etc. An alkali metal salt of an alkyl sulfonic acid having an alkyl group having 8 to 24 carbon atoms; an alkyl metal salt of an aromatic sulfonic acid such as phenyl sulfonic acid or naphthyl sulfonic acid; octyl phenyl sulfonic acid, dodecyl phenyl sulfonic acid, Alkali metal salts of alkylbenzene sulfonic acid having an alkyl group having 6 to 18 carbon atoms, such as dibutylphenyl sulfonic acid and dinonylphenyl sulfonic acid; dimethyl naphthyl sulfonic acid, diisopropyl naphthyl sulfonic acid, dibutyl naphthyl sulfonic acid, etc. Alkali metal salts of alkyl naphthalene sulfonic acids having an alkyl group having 2 to 18 carbon atoms; alkali metal salts of fluorinated sulfonic acids such as trifluoromethane sulfonic acid; alkali metal salts of tris (trifluoromethanesulfonyl) methane .
The said salts can be used individually by 1 type or in combination of 2 or more types.
The amount of the salt is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyamide-based elastomer and / or the polyether ester-based elastomer.

The refractive index of the component [B] at 25 ° C. is preferably 1.500 to 1.518, more preferably 1.510 to 1.518, and still more preferably 1.515 to 1.518.
In the case of forming a molded article having a transparent feeling or transparency, the absolute value of the difference between the refractive index of the component [A] and the refractive index of the component [B] is preferably 0.01 or less, more preferably 0. 0.008 or less, more preferably 0.005 or less, and particularly preferably 0.003 or less. The smaller this difference, the better the transparency.

1-3. Stretching Resin Composition In the composition of the present invention, the contents of the components [A] and [B] are 70 to 99% by mass and 30 to 30%, respectively, when the total amount is 100% by mass. 1% by mass, preferably 75 to 95% by mass and 25 to 5% by mass, more preferably 75 to 90% by mass and 25 to 10% by mass, still more preferably 75 to 85% by mass and 25 to 15% by mass. is there. If the content of the component [A] is too small, the rigidity and hardness are lowered, and the film, sheet, container and the like are easily deformed, which may cause trouble during use.

  The haze of the thin-walled body (thickness 0.03 to 0.1 mm) made of the composition of the present invention is preferably 10% or less, more preferably 8% or less.

  Depending on the purpose and application, the composition of the present invention may further comprise other antistatic agents, ultraviolet absorbers, weathering agents, fillers, antioxidants, anti-aging agents, flame retardants, antifogging agents, lubricants, antibacterial agents. Additives such as agents, tackifiers, plasticizers and colorants; may contain other polymers.

  Other antistatic agents include anionic antistatic agents such as sodium alkylsulfonate, sodium alkylbenzenesulfonate, alkylphosphate; phosphonium alkylsulfonate, phosphonium alkylbenzenesulfonate, tetraalkylammonium salt, trialkylbenzylammonium salt, Cationic antistatic agents such as quaternary ammonium salts; Nonionic antistatic agents such as polyhydric alcohol derivatives and alkylethanolamines; Amphoteric antistatic agents such as alkylbetaines and sulfobetaine derivatives; Complex compounds; Metal alkoxides and their Derivatives (alkoxysilane, alkoxytitanium, alkoxyzirconium, etc.); organic boron compounds; low molecular weight antistatic agents such as coated silica.

Examples of the ultraviolet absorber include benzophenones, benzotriazoles, salicylic acid esters, metal complex salts and the like. These can be used alone or in combination of two or more.
Content of the said ultraviolet absorber is 0.05-5 mass parts normally with respect to 100 mass parts of said component [A].

Examples of the weathering agent include organic phosphorus compounds, organic sulfur compounds, and organic compounds containing a hydroxyl group. These can be used alone or in combination of two or more.
Content of the said weathering agent is 0.1-5 mass parts normally with respect to 100 mass parts of said component [A].

Examples of the filler include talc, titanium oxide, clay, calcium carbonate and the like. These can be used alone or in combination of two or more.
Content of the said filler is 0.05-20 mass parts normally with respect to 100 mass parts of said component [A].

Examples of the antioxidant include hindered amines, hydroquinones, hindered phenols, and sulfur-containing compounds. These can be used alone or in combination of two or more.
Content of the said antioxidant is 0.1-3 mass parts normally with respect to 100 mass parts of said component [A].

Anti-aging agents include naphthylamine, diphenylamine, p-phenylenediamine, quinoline, hydroquinone derivatives, monophenol, bisphenol, trisphenol, polyphenol, thiobisphenol, hindered phenol, phosphorous acid Examples include ester compounds. These can be used alone or in combination of two or more.
Content of the said anti-aging agent is 0.1-3 mass parts normally with respect to 100 mass parts of said component [A].

As a lubricant, metal soap, higher fatty acid, fatty acid ester, oxy fatty acid, fatty acid amide, alkylene bis fatty acid amide, aliphatic ketone, fatty acid lower alcohol ester, fatty acid polyhydric alcohol ester, fatty acid polyglycol ester, aliphatic alcohol, polyhydric alcohol Examples include alcohol, polyglycol, polyglycerol, hydrocarbon resin, paraffin, silicone, and modified silicone. These can be used alone or in combination of two or more.
Examples of the metal soap include zinc stearate, zinc behenate, and magnesium behenate.
Examples of the higher fatty acid include compounds having 21 or more carbon atoms, such as behenic acid and montanic acid.
Examples of fatty acid esters include diesters of montanic acid and ethylene glycol.
The content of the lubricant is usually 0.3 to 3 parts by mass with respect to 100 parts by mass of the component [A]. By setting it as this range, peeling from the processing apparatus related to the stretching process can be facilitated. For example, when calendering is performed, if the content of the lubricant is small, the peelability of the molten resin is lowered, and the surface appearance of the thin body may be impaired. On the other hand, if the amount is too large, the thin body may bleed out, and secondary processing such as printing and adhesive coating may be difficult.

  Other polymers include polycarbonate, polypropylene, polyethylene and the like.

  The refractive index at 25 ° C. of the resin composition for stretch processing of the present invention is preferably 1.500 to 1.518, more preferably 1.510 to 1.518, and still more preferably 1.515 to 1.518. is there.

  The resin composition for stretch processing of the present invention comprises the above-mentioned components [A] and [B], and further additives, other polymers, etc., blended as necessary, various extruders, Banbury mixers, kneaders. It can be produced as pellets by being put into a continuous kneader, roll or the like and melt-kneaded under heating. Each component may be mixed and then kneaded, or may be divided and added. Further, when kneading, two or more kinds of kneading apparatuses may be connected.

The resin composition for stretch processing of the present invention comprises a grafted rubbery polymer grafted with a copolymer of a vinyl monomer (b) formed during the production of a rubber-reinforced copolymer resin (A1), A copolymer of vinyl monomer (b) that is not used and component [B].
The number average particle diameter of the grafted rubbery polymer is usually 100 to 800 nm, preferably 200 to 400 nm. The number average particle diameter of the grafted rubbery polymer was observed by a transmission electron microscope after dyeing a flake made of the composition of the present invention by immersing it in a solution of OsO ₄ or RuO ₄ . For example, the average value of the particle diameters measured for 100 particles can be used.

The resin composition for stretch processing of the present invention is suitable for producing a molded product by a method such as calendar molding, inflation molding, T-die molding, or vacuum molding. In particular, calendar molding is preferable, and the effect of improving antistatic performance by stretching is excellent.
In addition, the resin composition for stretch processing of the present invention is more charged when molded at a stretch ratio of preferably 1.5 to 20 times, more preferably 1.5 to 10 times, and even more preferably 2 to 8 times. Excellent improvement in prevention performance. Therefore, it is suitable as a molding material for extrusion molding to which the above draw ratio is applied.
In the present specification, “stretch ratio” refers to the stretched portion of the molded article of the present invention obtained by various processing methods, and the thickness before stretching is the thickness after stretching as in the following formula. It means the value divided.
Stretch ratio = (Thickness before stretching) / (Thickness after stretching)

  Accordingly, the resin molding composition for stretch processing according to the present invention is calender-molded with a stretch ratio of preferably 1.5 to 20 times, more preferably 1.5 to 10 times, and even more preferably 2 to 8 times. It is suitable when used as a molding material.

2. Molded body The molded body of the present invention comprises the above-described resin composition for stretch processing of the present invention, has a thin-walled portion having a stretch ratio of 1.5 to 20 times in at least one place, and the surface resistivity of the thin-walled portion. Is 1 × 10 ¹¹ Ω or less.

  A thin part may be a part in the molded object of this invention, and may be the whole. Therefore, it may be a molded body having a thin portion such as a dot shape, a linear shape, a planar shape, or an indefinite shape, or a molded body 1 (see FIG. 1) that is a thin portion by stretching the entire film, sheet, or the like. There may be. The latter molded body may be flat or curved.

The thickness of the thin portion is preferably 0.05 to 1.5 mm, more preferably 0.05 to 1 mm, and still more preferably 0.05 to 0.8 mm. When this thickness is too thin, the network of the component [B] is not formed, and the antistatic performance may deteriorate.
Moreover, a draw ratio is 1.5-20 times, Preferably it is 1.5-10 times, More preferably, it is 2-8 times. If this stretch ratio is too small, the antistatic performance tends to be reduced, whereas if it is too large, the network of component [B] is not formed, and the antistatic performance tends to be reduced. The stretching direction may be uniaxial or biaxial.

The surface specific resistance of the thin portion is a value measured under conditions of a temperature of 23 ° C. and a relative humidity of 50%. The resistance is 1 × 10 ¹¹ Ω or less, preferably 9 × 10 ¹⁰ Ω or less, more preferably 5 × 10 ¹⁰ Ω or less. In addition, the surface specific resistance in the part other than the thin part, that is, the stretch ratio is not 1.5 to 20 times, is usually a high value exceeding 1 × 10 ¹¹ Ω.

  The molded body of the present invention may be provided with a recess, a groove, a through hole, or the like on at least a part of the surface depending on the purpose, application, or the like. These parts may be on the thin part or may be in a place other than the thin part.

The molded body of the present invention is preferably produced by a method such as calendar molding, inflation molding, T-die molding, or vacuum molding. According to these methods, the effect of the component [B] contained, that is, the antistatic performance is sufficiently exhibited. In particular, in the case of a calendar molding method, the performance can be exhibited to a high degree.
Moreover, after each said shaping | molding method, it can also be set as a molded object provided with a desired shape, a site | part, etc. by the process according to the objectives, uses, etc., such as cutting | disconnection and adhesion | attachment.

  The molded body of the present invention can be used as a film, a sheet, a container and the like. Therefore, it is suitable as a packaging body for electronic parts, electronic devices, etc., a container (tray, etc.), a protective member, a partition; an underlay used when cutting various members, etc .; a clean room structural member (wall, curtain, etc.) It is.

  When a film and a sheet are formed by calendering, usually, each step and means for mixing raw materials constituting the composition of the present invention, preliminary kneading, calendering (rolling), cooling and winding are sequentially provided. A calendar forming apparatus is used.

  In the preliminary kneading step, a hot roll or the like adjusted to a temperature considering the melting temperature of the component [A] or the like is usually used. Thereafter, the kneaded product is filtered through a filter or the like in order to remove impurities and the like, and is supplied to a calendar device by an extruder or the like.

In the case of calendar processing, a calendar (apparatus) having two or more calendar rolls such as an L-type, an inverted L-type, a Z-type, an inclined Z-type, an upright three-type, and an inclined two-type is used. This calendar (apparatus) may further include a pressing roll independent of the calendar roll. The molten or semi-molten kneaded material introduced between the calender rolls is rolled into a film or the like. The calendar roll may be heated. Moreover, when rolling by a plurality of calendar rolls such as L-type, reverse L-type, Z-type, and inclined Z-type, the temperature may be set to decrease from the front stage to the rear stage of the roll.
FIG. 2 is a schematic view of a calendar device 3 for producing a film or a sheet. A kneaded material is introduced between the first roll 31 and the second roll 32 and is pushed downward while forming the bank 6. A film is formed. Then, it is stretched by the third roll 33 and the fourth roll 34 to obtain the molded body of the present invention.
The rotation speed of each calendar roll is usually selected in the range of 10 to 60 m / min, preferably 15 to 50 m / min.

Thereafter, the formed film or the like is cooled by a method of sending it to the next step under a low temperature atmosphere using a cooling device, a blower device or the like, a method of sending it through a cooling roll, or the like.
Furthermore, it winds up using a well-known winding apparatus etc.

  When producing a molded body, for example, an antistatic film, by inflation molding or T-die molding, a known apparatus is used to melt the composition of the present invention at a temperature of 200 to 250 ° C. to form a film. Thus, a stretched film can be obtained.

  In the case of producing a molded body, for example, a tray by vacuum forming, after obtaining a sheet using the composition of the present invention, preheating at a temperature of about 400 ° C. and performing vacuum forming so as to have a predetermined shape. Thus, a molded article having excellent antistatic performance can be obtained.

  Hereinafter, the present invention will be described more specifically with reference to examples. In Examples and Comparative Examples, parts and% are based on mass unless otherwise specified.

The measuring method of various evaluation items is as follows.
(1) Surface resistivity (Ω)
The surface resistivity of the stretched film (10 cm × 10 cm) on the surface of the antistatic layer was measured under the same conditions after standing for 7 days at a temperature of 23 ° C. and a relative humidity of 50%. The measuring device is an Agilent high resistance meter (models “4339B” and “16008B”).
(2) Haze value The haze value of a stretched film (5 cm × 4 cm) was measured under the same conditions after standing for 2 days at a temperature of 23 ° C. and a relative humidity of 50%. The measuring device is a hedometer (trade name “haze-gard plus”) manufactured by Gardner.
(3) Outgas amount (μg / g)
50 mg of the stretched film was used as a measurement sample. The measurement sample was filled in a heating purge tube so as to be sandwiched between 10 mg of silane-treated quartz wool and accommodated in a heating furnace. Thereafter, while flowing helium gas (flow rate: 50 ml / min), the temperature was maintained at 25 ° C. for 1 minute, then heated to 150 ° C. at a temperature rising rate of 60 ° C./minute, and further maintained for 30 minutes. The outgas released from the measurement sample by this heating was analyzed by a gas chromatograph measuring apparatus (model “5890 SERIES II”) manufactured by Agilent. The total amount of all the detected components until the retention time reaches 30 minutes was converted into an n-octane amount, which was defined as “outgas amount”.

(4) Rockwell hardness Using an injection molding machine with a cylinder molding temperature of 200 ° C., a test piece having a length of 80 mm, a width of 40 mm and a thickness of 3.04 mm was prepared, and two of them were stacked to form ISO 2039 (Scale R). According to, it used for the measurement.
First, an indenter (diameter 12.7 mm) is used on the surface of the test piece, a reference load (98.07 N) is added thereto, a test load (588.4 N) is then added, and then the reference load is again applied. Was added, and the penetration depth of the indenter at the reference load twice before and after was measured, and the Rockwell hardness (HR) was determined by the following formula using the average value of three measurements each.
HR = 130-500h
(H is the difference in indentation depth of the indenter at the standard load twice (front and rear) (mm))

1. Ingredient [A]
A copolymer resin and a copolymer obtained by the following production method were used.

Production Example 1 (Production of copolymer resin [A1-1])
In a 7-liter glass flask equipped with a stirrer, 100 parts of ion-exchanged water, 2 parts of potassium rosinate, 0.5 part of tert-dodecyl mercaptan, 30 parts of butadiene rubber latex (in terms of solid content), 16 parts of styrene, 5 parts of acrylonitrile and 49 parts of methyl methacrylate were added, and the temperature was raised while stirring. When the temperature reaches 50 ° C., it consists of 0.2 parts of ethylenediaminetetraacetate, 0.05 parts of ferrous sulfate, 0.2 parts of sodium formaldehyde sulfoxylate dihydrate and 10 parts of ion-exchanged water. An aqueous activator solution and 0.2 part of diisopropylbenzene hydroperoxide were added to initiate the polymerization reaction, and then allowed to react for 6 hours. The polymerization conversion of the monomer was 96%.
Next, the reaction product latex was coagulated with a 36% aqueous calcium chloride solution at 90 ° C., and the resulting slurry was heated to 95 ° C. and held for 5 minutes. Then, washing with water and further drying at 75 ° C. for 24 hours gave a powdery copolymer resin [A1-1]. The graft ratio of this copolymer resin [A1-1] was 35%, the intrinsic viscosity [η] of the acetone-soluble component was 0.28 dl / g, and the refractive index at 25 ° C. was 1.516.

Production Example 2 (Production of copolymer resin [A1-2])
In a 7-liter glass flask equipped with a stirrer, 100 parts of ion exchange water, 1 part of potassium rosinate, 0.5 part of tert-dodecyl mercaptan, 18 parts of butadiene rubber latex (in terms of solid content), 20 parts of styrene and 62 parts of methyl methacrylate was added and the temperature was increased while stirring. When the temperature reaches 50 ° C., it comprises 0.2 parts of ethylenediaminetetraacetate, 0.01 parts of ferrous sulfate, 0.2 parts of sodium formaldehyde sulfoxylate dihydrate and 10 parts of ion-exchanged water. An aqueous activator solution and 0.2 part of cumene hydroperoxide were added to initiate the polymerization reaction, and then reacted for 6 hours. The polymerization conversion of the monomer was 96%.
Next, the reaction product latex was coagulated with a 36% aqueous calcium chloride solution at 90 ° C., and the resulting slurry was heated to 95 ° C. and held for 5 minutes. Then, washing with water and further drying at 75 ° C. for 24 hours gave a powdery copolymer resin [A1-2]. The graft ratio of this copolymer resin [A1-2] was 38%, the intrinsic viscosity [η] of the acetone-soluble component was 0.27 dl / g, and the refractive index at 25 ° C. was 1.516.

Production Example 3 (Production of copolymer resin [A1-3])
In a 7-liter glass flask equipped with a stirrer, in a nitrogen stream, 75 parts of ion exchange water, 0.5 part of potassium rosinate, 0.1 part of tert-dodecyl mercaptan, butadiene rubber latex (average particle size: 350 nm) Gel content: 85%) 40 parts (in terms of solid content), 15 parts of styrene and 5 parts of acrylonitrile were added, and the temperature was increased while stirring. When the temperature reached 45 ° C., an aqueous activator solution consisting of 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate, 0.2 parts of glucose and 20 parts of ion-exchanged water was added. . Thereafter, 0.07 part of cumene hydroperoxide was added to initiate polymerization.
After polymerizing for 1 hour, 50 parts of ion exchange water, 0.7 parts of potassium rosinate, 30 parts of styrene, 10 parts of acrylonitrile, 0.05 part of tert-dodecyl mercaptan and 0.01 part of cumene hydroperoxide for 3 hours. The polymerization was continuously added over 1 hour, and the polymerization was continued for another hour. Next, 0.2 part of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) was added to complete the polymerization.
Thereafter, the reaction product latex was coagulated with an aqueous sulfuric acid solution, and the resulting slurry was washed with water and further dried to obtain a powdery copolymer resin [A1-3]. The graft ratio of this copolymer resin [A1-3] was 68%, the intrinsic viscosity [η] of the acetone-soluble component was 0.45 dl / g, and the refractive index was opaque and could not be measured.

Production Example 4 (Production of copolymer [A2-1])
Two jacketed polymerization reaction vessels equipped with ribbon wings with an internal volume of 30 liters were connected and purged with nitrogen, and then the first reaction vessel was 21 parts styrene, 7 parts acrylonitrile, 72 parts methyl methacrylate and 20 parts toluene. Were continuously charged. Thereafter, a solution in which 0.1 part of tert-dodecyl mercaptan was dissolved in 5 parts of toluene as a molecular weight regulator, and 0.1 part of 1,1′-azobis (cyclohexane-1-carbonitrile) as a polymerization initiator were added. A solution dissolved in 5 parts of toluene was continuously supplied, the polymerization temperature in the first reaction vessel was controlled at 110 ° C., and polymerization was carried out with an average residence time of 2 hours. The polymerization conversion rate was 60%.
Next, the same amount as the total supply amount of styrene, acrylonitrile, methyl methacrylate, toluene, molecular weight regulator and polymerization initiator is continuously added from the obtained polymerization solution by a pump provided outside the first reaction vessel. Was taken out into a second reaction vessel. The polymerization temperature in this second reaction vessel was controlled at 130 ° C., and polymerization was carried out with an average residence time of 2 hours. The polymerization conversion was 80%.
Thereafter, the polymerization solution is taken out from the second reaction vessel and directly introduced into an extruder with a biaxial three-stage vent to remove unreacted monomers and solvent, and a styrene / acrylonitrile / methyl methacrylate copolymer [ A2-1] was obtained. The intrinsic viscosity [η] of the acetone solution of the copolymer [A2-1] was 0.25 dl / g, and the refractive index at 25 ° C. was 1.516.

  As the copolymer [A2-2], a styrene / acrylonitrile copolymer obtained by solution polymerization in a toluene solvent and containing styrene units and acrylonitrile units in a mass ratio of 75:25 was used. The intrinsic viscosity [η] of the acetone solution of the copolymer [A2-2] is 0.35 dl / g, and the refractive index at 25 ° C. is 1.573.

2. Ingredient [B]
(1) [B-1]
PA6 polyamide elastomer composed of a hard segment made of polyamide 6 and a soft segment made of poly (alkylene oxide) glycol polymer (melting point 195 ° C., refractive index 1.514 at 25 ° C., reduced viscosity 1 at 25 ° C. 1 .51 dl / g (measured using 0.5 g / 100 ml formic acid solution), surface resistivity 4 × 10 ¹⁰ Ω) was used.
(2) [B-2]
PA12 polyamide elastomer composed of a hard segment made of polyamide 12 and a soft segment made of a poly (alkylene oxide) glycol polymer (melting point 148 ° C., refractive index 1.514 at 25 ° C., reduced viscosity 1 at 25 ° C. 1 .51 dl / g (measured using 0.5 g / 100 ml formic acid solution), surface resistivity 3 × 10 ¹⁰ Ω) was used.

3. Lubricant (component [C])
Zinc behenate (“ZS-7” manufactured by Nitto Kasei Kogyo Co., Ltd.) was used.

4). Preparation and Evaluation of Stretching Resin Composition Using the above components, a stretching process resin composition was prepared and subjected to various evaluations.
Examples 1-9 and Comparative Examples 1-4
Each component was mixed by the Henschel mixer in the ratio of Table 1 and Table 2. Thereafter, this mixture was put into a twin screw extruder and melt-kneaded at a temperature of 200 to 240 ° C. to obtain pellets (stretching resin composition). Component [C] was used in an amount of 0.7 part with respect to 100 parts of component [A].

Next, using the pellets, stretched films F1 to F13 were prepared by the following method, and the surface resistivity, haze value, outgas amount, and Rockwell hardness were measured.
First, the pellets were melt-kneaded at 180 to 190 ° C. using a hot roll. Thereafter, the kneaded product was supplied to an extruder equipped with five 20, 60, 350, 60, and 20 mesh filters, and melt-kneaded at 210 ° C. Next, the kneaded material is supplied between the first roll 31 and the second roll 32 of the calendar apparatus including the inverted L-shaped four calendar rolls shown in FIG. A stretched film having the thickness described in 2 was obtained. The evaluation results are shown in Tables 1 and 2.
The draw ratio is adjusted by appropriately adjusting the discharge amount from the extruder, the roll interval between the second roll and the third roll, the roll interval between the third roll and the fourth roll, the rotation speed of each roll, the winding speed of the stretched film, etc. , Made by choosing. The draw ratio is a value obtained by dividing the roll interval between the first roll and the second roll by the thickness before stretching (ignoring molding shrinkage of the resin) and dividing by the thickness of the finally obtained stretched film.

Comparative Example 3 is an example using a composition containing no component [B], and the surface resistivity exceeded 10 ¹⁴ Ω. Comparative Example 4 is an example containing a large amount of component [B], and the hardness is inferior.
Comparative Examples 1 and 2 are examples of molded articles having a low draw ratio of 1.2 times, although the compositions within the scope of the present invention were used, and the surface resistivity was 2.0 × 10 ¹¹ respectively. Ω and 3.0 × 10 ¹¹ Ω are large.
On the other hand, Examples 1 to 9 are examples in which the draw ratio is 2 to 6 times, and even if the content ratios of the components [A] and [B] are the same, the surface specific resistance is lowered and the antistatic property is improved. It turns out that it is excellent.

  The stretchable resin composition of the present invention is suitable for molded articles such as films, sheets, and containers, and in particular, electronic parts, packaging bodies such as electronic devices, containers (tray etc.), protective members, partitions; Underlay used when cutting various members, etc .; useful for structural members (walls, curtains, etc.) in clean rooms. Furthermore, tapes (including adhesive tape); films (including adhesive film, laminate film, masking film, wallpaper film, decorative paper, decorative paper substitute film, interior film, exterior film, bag, etc.); Sheets for home use, electronic equipment storage or electronic equipment installation; pens with thin-walled parts, stationery such as files, refrigerator, washing machine, dryer, vacuum cleaner, fan, air conditioner, telephone, electric kettle, rice cooker , Dishwashers, dish dryers, microwave ovens, mixers, televisions, videos, stereos, tape recorders, watches, computers, displays, calculators and other household appliances, vehicle-related parts, medical equipment, optical equipment, etc. Can also be used.

It is sectional drawing which shows an example of the molded object (stretched sheet) of this invention. It is the schematic which shows the manufacturing method of the molded object (stretched film) in an Example.

Explanation of symbols

1: Molded body (stretched sheet or stretched film)
3; reverse L-shaped calendar 31; first roll 32; second roll 33; third roll 34; fourth roll 6;

Claims (8)

[A] A vinyl type containing an aromatic vinyl compound and at least one compound selected from a vinyl cyanide compound, a (meth) acrylic ester compound and a maleimide compound in the presence of the rubbery polymer (a). A rubber-reinforced copolymer resin (A1) obtained by polymerizing the monomer (b), or a copolymer (A2) of the rubber-reinforced copolymer resin (A1) and the vinyl monomer (b). 70 to 99% by mass of a styrene rubber-reinforced resin comprising a mixture of
[B] 30 to 1% by mass of a polymeric antistatic agent (provided that [A] + [B] = 100% by mass);
A resin composition for drawing processing, comprising:   The resin composition for drawing processing according to claim 1, wherein the polymer antistatic agent [B] is a polyamide-based elastomer and / or a polyetherester-based elastomer.   The resin composition for stretching processing according to claim 1 or 2, wherein the haze of a thin-walled body having a thickness of 0.03 to 0.1 mm is 10% or less.   The absolute value of the difference between the refractive index at 25 ° C of the styrene rubber-reinforced resin [A] and the refractive index at 25 ° C of the polymeric antistatic agent [B] is 0.01 or less. 4. The resin composition for stretching processing according to any one of 3 above. 5. The resin composition for stretch processing according to claim 1, comprising a thin portion having a draw ratio of 1.5 to 20 times in at least one location, and the surface resistivity of the thin portion is 1 × 10 ¹¹ Ω or less.   The molded body according to claim 5, wherein the thin portion is formed by a method selected from calendar molding, inflation molding and vacuum molding.   The molded body according to claim 5 or 6, wherein the molded body is selected from a film, a sheet, and a container.   The molded product according to claim 7, which is used for an electronic component or an electronic device.

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