JP5158976B2 - Antistatic resin composition, antistatic resin molded body, and antistatic resin laminate - Google Patents

Description

  The present invention relates to an antistatic resin composition, an antistatic resin molded body, and an antistatic resin laminate.

  In general, a sheet or a molded body formed of a thermoplastic resin has a high surface resistivity and is very easily charged. Therefore, a lens module, a display panel, a packaging material for semiconductors and electronic components (for example, these optical or When used as an embossed carrier tape, tray, magazine, or other container or sheet for transporting electronic materials), dust adheres due to static electricity, and damage or destruction of electronic materials due to static electricity occurs. Therefore, it is necessary to impart antistatic properties to these packaging materials at least up to the antistatic level.

  Conventionally, as a means for imparting antistatic properties, for example, a technique of blending an antistatic agent such as polyetheresteramide with a thermoplastic resin has been proposed (see, for example, Patent Documents 1 to 3). In particular, it is disclosed in the Examples that blending an antistatic agent with ABS resin suppresses carbon adhesion and provides stable antistatic performance.

  Further, a styrene thermoplastic elastomer having a styrene content of 6 to 60% by mass, a softening material for rubber, a peroxide-decomposable polyolefin resin, a block mainly composed of an olefin component and a block mainly composed of a hydrophilic component. A thermoplastic elastomer composition containing an inhibitor has been proposed (see, for example, Patent Document 4).

Japanese Patent Laid-Open No. 7-10989 JP 2002-146212 A JP 2006-15741 A JP 2003-306584 A

  However, in the above prior art, it is possible to suppress the adhesion of dust from the outside by increasing the antistatic property. On the other hand, when used as a packaging material, it is easily damaged when it is rubbed with a product during transportation. There has been a problem that the resin (shaving residue) scraped off becomes dust and easily adheres to the product.

  The present invention has been made in view of the above problems, and its purpose is not only excellent in antistatic properties, but also antistatic resin compositions and antistatic resin molded bodies that are less likely to cause scraping when scratched, and An antistatic resin laminate is provided.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by using a resin composition in which a block copolymer having a specific structure and an antistatic agent are blended at a predetermined ratio. The invention has been completed.

That is, the present invention provides the following [1] to [9]: [1] At least one polymer block A mainly composed of vinyl aromatic hydrocarbon and at least one polymer mainly composed of conjugated diene The average particle size of at least one block copolymer (a), styrene resin (b), and rubber particles, which is composed of block B and has a vinyl aromatic hydrocarbon content of 60 to 95% by mass, is 0.5. The impact-resistant polystyrene resin (c) which is ˜5 μm and the antistatic agent (d) having a polyoxyethylene chain are contained, and the contents of these (a), (b), (c) and (d) There (a) / (b) / (c) / (d) = 20~90 wt% / 0-70 mass% / 0-20 mass% / 5 to 80% by mass is, furthermore, a styrene - butadiene block Hydrogenated copolymer and / or styrene-butadi Acid anhydride group-modified product of emissions block copolymer above (a), the (b), Rukoto contains 3 to 30 parts by weight of the resin composition 100 parts by mass consisting of (c) and (d) Features
Antistatic resin composition.

[2] In the block copolymer (a), the proportion of the vinyl aromatic hydrocarbon polymer block is 60% by mass or more of the total vinyl aromatic hydrocarbon in the block copolymer.
Antistatic resin composition as described in said [1].

[3] The styrenic resin (b) comprises at least one polymer block C composed of vinyl aromatic hydrocarbons and at least one copolymer block D mainly composed of vinyl aromatic hydrocarbons, At least one block copolymer component (b-B) having a vinyl aromatic hydrocarbon content of 60 to 95% by mass,
Antistatic resin composition as described in said [1] or [2].

[4] The antistatic agent (d) is a polyetheresteramide.
Antistatic resin composition as described in any one of said [1]-[3].

[5] The antistatic agent (d) is a block polymer having a structure in which a block of polyolefin and a block having a polyoxyethylene chain are repeatedly and alternately bonded.
Antistatic resin composition as described in any one of said [1]-[3].

[6] The antistatic resin composition according to any one of [1] to [5] above ,
Antistatic resin molding.

[7] The antistatic resin composition (A) according to any one of [1] to [5] , which is formed on one side of the base material layer made of the thermoplastic resin (B) and the base material layer. And a surface layer made of
Antistatic resin laminate.

[8] The thickness of the surface layer (A) is 5 μm to 0.2 mm.
The antistatic resin laminate according to [7] above.

  According to the present invention, an antistatic resin composition, an antistatic resin molded body, and an antistatic resin laminate that are not only excellent in antistatic properties but are less prone to scraping are realized.

  Embodiments of the present invention will be described below. In addition, the following embodiment is an illustration for demonstrating this invention, and this invention is not limited only to the embodiment.

  The antistatic resin composition of the present embodiment includes a specific block copolymer (a), a styrene resin (b), and an impact-resistant polystyrene resin (c) whose rubber particles have an average particle diameter of 0.5 to 5 μm. ), And an antistatic agent (d) having a polyoxyethylene chain, and the contents of (a), (b), (c), and (d) are (a) / (b) / (c ) / (D) = 20 to 90% by mass / 0 to 70% by mass / 0 to 20% by mass / 5 to 80% by mass.

  The block copolymer (a) used in this embodiment comprises at least one polymer block A mainly composed of vinyl aromatic hydrocarbons and at least one polymer block B mainly composed of conjugated diene, It is a block copolymer having a vinyl aromatic hydrocarbon content of 60 to 95% by mass.

  Here, the polymer block A mainly composed of a vinyl aromatic hydrocarbon is a copolymer block of a vinyl aromatic hydrocarbon and a conjugated diene having a vinyl aromatic hydrocarbon content of 50% by mass or more, and / or Alternatively, it means a homopolymer block of vinyl aromatic hydrocarbon.

  The polymer block B means a copolymer block of a vinyl aromatic hydrocarbon and a conjugated diene containing more than 50% by mass of a conjugated diene compound and / or a homopolymer block of a conjugated diene compound.

  In the block copolymer (a) used in the present embodiment, the proportion of the vinyl aromatic hydrocarbon content is preferably 60 to 95% by mass, more preferably 70 to 80% by mass. In the range of 60 to 95% by mass, it is difficult for scraps to be generated when the resulting resin molded body is rubbed, and it is difficult for the scraps of the resin molded body to adhere to the product when used as a packaging container or the like. Moreover, if it is 60 mass% or more, the resin molded body which is excellent in rigidity will be easy to be obtained, for example, when using as a packaging container etc., it will become difficult to collapse. Further, if it is 95% or less, a resin molded article having excellent strength is easily obtained. For example, when it is used as a packaging container or the like, deformation hardly occurs, and it becomes difficult to break when dropped. If it is 70 to 80% by mass, a good balance between rigidity and strength can be obtained.

  When a random copolymer portion of vinyl aromatic hydrocarbon and conjugated diene exists in polymer block A mainly composed of vinyl aromatic hydrocarbon or polymer block B mainly composed of conjugated diene, In the coalescence part, the vinyl aromatic hydrocarbon copolymerized may be distributed uniformly in the polymer block or may be distributed in a taper (gradual decrease). In addition, the random polymer portion may coexist with a portion where the vinyl aromatic hydrocarbon is uniformly distributed and / or a portion where the portion is distributed in a tapered shape.

  When the block copolymer (a) has a plurality of polymer blocks A (or B), they may have different molecular weights, compositions, types, and the like.

The block copolymer (a) can be produced by a conventionally known method. For example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-171979, Japanese Patent Publication No. 48-2423, Japanese Patent Publication No. 49- Techniques described in Japanese Patent No. 36957, Japanese Patent Publication No. 57-49567, Japanese Patent Publication No. 58-11446, and the like can be applied. All of the above known methods are methods in which a conjugated diene and a vinyl aromatic hydrocarbon are block copolymerized using an anionic initiator such as an organolithium compound in a hydrocarbon solvent. The polymer structure of the block copolymer (a) used in the present embodiment is, for example,
A- (BA) _n , A- (BA) _n- B, B- (AB) _{n + 1} ... (I)
[In the above formula (I), A is a polymer block mainly composed of vinyl aromatic hydrocarbons, and B is a polymer block mainly composed of conjugated dienes. n is an integer greater than or equal to 1, and is generally 1-5. ]
Or a linear block copolymer represented by
[(A−B) _k ] _{m + 2} −X, [(A−B) _k −A] _{m + 2} −X, [(B−A) _k ] _{m + 2} −X (II)
[(B−A) _k −B] _{m + 2} −X (III)
[In the said (II) Formula and (III), A and B are the same as said (I), k and m are integers greater than or equal to 1, and are generally 1-5. X represents a residue of a coupling agent such as silicon tetrachloride or tin tetrachloride or a residue of an initiator such as a polyfunctional organolithium compound. ]
The radial block copolymer represented by these. Further, two or more kinds of the block copolymers (a) may be mixed and used.

  Specific examples of the vinyl aromatic hydrocarbon include, for example, styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, Examples include 1,1-diphenylethylene, but are not particularly limited thereto. Among these, styrene and p-methylstyrene are preferable. These can be used individually by 1 type or in mixture of 2 or more types.

  Conjugated dienes are diolefins having a pair of conjugated double bonds, and specific examples thereof include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl- 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene and the like can be mentioned, but not limited thereto. Among these, 1,3-butadiene and isoprene are preferable. These can be used individually by 1 type or in mixture of 2 or more types.

  When 1,3-butadiene and isoprene are used in combination as the conjugated diene, the amount of 1,3-butadiene is preferably 10% by mass or more, more preferably 25% by mass or more, and further preferably 40% by mass or more. When 1,3-butadiene is 10% by mass or more, thermal decomposition does not occur at the time of molding or the like and the molecular weight does not decrease, so that it can be preferably used as a styrene resin sheet.

  Specific examples of the hydrocarbon solvent include, for example, aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, and octane, and alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane. , Aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene and the like, but are not particularly limited thereto. These can be used individually by 1 type or in mixture of 2 or more types.

  Examples of the organic lithium compound include organic monolithium compounds, organic dilithium compounds, and organic polylithium compounds in which one or more lithium atoms are bonded in the molecule, and more specifically, ethyl lithium, n-propyl lithium, and the like. , Isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, hexamethylene dilithium, butadienyl dilithium, isoprenyl dilithium and the like, but are not particularly limited thereto. These can be used individually by 1 type or in mixture of 2 or more types.

  When the block copolymer (a) is produced, the polymerization rate is adjusted, the microstructure of the polymerized conjugated diene part (cis, trans, vinyl ratio) is adjusted, and the reaction ratio between the conjugated diene and the vinyl aromatic hydrocarbon is adjusted. For the purpose of adjustment, polar compounds and randomizing agents can be used. Specific examples of polar compounds and randomizing agents include, for example, ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, amines such as triethylamine, tetramethylethylenediamine, thioethers, phosphines, phosphoramides, alkylbenzene sulfonates. , Alkoxides of potassium and sodium, and the like, but are not particularly limited thereto. These can be used individually by 1 type or in mixture of 2 or more types.

  The polymerization temperature for producing the block copolymer (a) is generally in the range of −10 to 150 ° C., preferably 40 to 120 ° C. The polymerization time varies depending on the conditions, but is usually within 48 hours, preferably in the range of 1 to 10 hours. The polymerization atmosphere is preferably replaced with an inert gas such as nitrogen gas. The polymerization pressure may be in a range sufficient to maintain the monomer and solvent in the liquid layer within the above polymerization temperature range, and is not particularly limited. In the polymerization, care must be taken not to mix impurities that inactivate the catalyst and living polymer, such as water, oxygen, and carbon dioxide, into the polymerization system.

  In the block copolymer (a), the proportion of the vinyl aromatic hydrocarbon polymer block is 60% by mass or more of the total vinyl aromatic hydrocarbon (hereinafter, the vinyl aromatic carbonization in the block copolymer (a)). The ratio of the hydrogen polymer block is taken as the block ratio). If it is 60% by mass or more, a resin molded product having excellent heat resistance can be easily obtained, and, for example, when used as a packaging container or the like, it is difficult to be deformed even at high temperatures during transportation in midsummer.

  The block ratio of the vinyl aromatic hydrocarbon block is such that at least a part of the vinyl aromatic hydrocarbon and the conjugated diene are copolymerized in the step of producing the block copolymer (a). It can be controlled by changing the mass ratio or the polymerization reactivity ratio. Specifically, for example, (b) a mixture of a vinyl aromatic hydrocarbon and a conjugated diene is continuously supplied to the polymerization system for polymerization, and (b) a vinyl aromatic using a polar compound or a randomizing agent. A method such as copolymerizing a hydrocarbon and a conjugated diene can be appropriately employed.

The block ratio of the vinyl aromatic hydrocarbon polymer block incorporated in the block copolymer (a) is determined by oxidative decomposition of the block copolymer with di-tertiary butyl hydroperoxide using osmium tetroxide as a catalyst. Method [I. M.M. KOLTHOFF, et al. , J .; Polym. Sci. 1,429 (1946)] is determined by quantifying the vinyl aromatic hydrocarbon polymer block component (excluding vinyl aromatic hydrocarbon polymer components having an average degree of polymerization of about 30 or less). And the value obtained from the following equation.

Vinyl aromatic of block copolymer
Mass% of hydrocarbon polymer block
Block ratio (mass%) = ――――――――――――――――― × 100
All vinyl block copolymer
% By mass of aromatic hydrocarbon

  The preferable compounding quantity of a block copolymer (a) is 20-90 mass%, More preferably, it is 30-75 mass%. In 20-90 mass%, the resin molding which is excellent in rigidity is easy to be obtained. Moreover, the resin molding which is excellent in intensity | strength is easy to be obtained by setting it as 30-75 mass%.

  The styrene resin (b) is obtained by polymerizing styrene or a monomer copolymerizable therewith. Examples of the monomer copolymerizable with styrene include, for example, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, 1,1. -Diphenylethylene, acrylic acid, methacrylic acid, acrylonitrile, acrylic acid ester, methacrylic acid ester, maleic anhydride and the like can be mentioned, but not limited thereto. Specific examples of the styrene resin include, for example, polystyrene, styrene-α-methylstyrene copolymer, styrene-methacrylic acid copolymer, acrylonitrile-styrene copolymer, styrene-methyl methacrylate copolymer, styrene-butyl acrylate. A copolymer, a styrene-maleic anhydride copolymer and the like can be mentioned, but the invention is not particularly limited thereto. Among these, polystyrene, styrene-methyl methacrylate copolymer, and styrene-butyl acrylate copolymer are preferable.

  The monomer copolymerizable with styrene includes a conjugated diene compound. The styrenic resin (b) in this case consists of a polymer block C composed of at least one vinyl aromatic hydrocarbon and a copolymer block D mainly composed of at least one vinyl aromatic vinyl aromatic hydrocarbon. And a block copolymer (b-B) having a vinyl aromatic hydrocarbon content of 60 to 95% by mass. The block copolymer (b) can be synthesized using a method similar to the method shown in the method for producing the copolymer (a).

  When the monomer copolymerizable with styrene is a conjugated diene compound, it is preferable because of excellent molding processability.

  The preferable compounding quantity of a styrene-type resin (b) is 0-70 mass%, More preferably, it is 20-60 mass%. By blending the styrene resin, the rigidity of the obtained resin molded body can be adjusted as appropriate. In the range of 0 to 70% by mass, it is difficult to produce scraps when the resulting resin molded body is rubbed. For example, when used as a packaging material, it is difficult to be damaged when rubbed with a product during transportation. It becomes difficult for the scrap to stick to the product.

  The high-impact polystyrene resin (c) is obtained by dissolving a butadiene-based rubber-like polymer in styrene, starting polymerization of styrene, and grafting the styrene to the rubber-like polymer. A rubber particle having an average particle diameter in the range of 0.5 μm to 5 μm is used as the impact resistant polystyrene resin (c). In the range of 0.5 μm to 5 μm, the resulting resin molded body is difficult to block, and the transparency when molded into a thin wall is difficult to be inhibited. The average particle diameter of the rubber particles is preferably 1.5 μm to 4 μm, and in this range, a resin molded body or a resin molded sheet excellent in impact resistance and bending resistance can be easily obtained. The average particle diameter of the rubber particles can be measured with a Coulter counter.

  The preferable compounding quantity of an impact-resistant polystyrene resin (c) is 0-20 mass%, More preferably, it is 1.5-15 mass%. In the range of 0 to 20% by mass, the transparency when formed into a thin wall is hardly impaired. Moreover, by setting it as 1.5-15 mass%, blocking is suppressed and the resin molded object and resin molded sheet which are excellent in transparency, impact resistance, and bending resistance are easy to be obtained.

  As the antistatic agent (d), a block polymer having a structure in which a block of polyetheresteramide and polyolefin and a block having a polyoxyethylene chain are alternately and repeatedly bonded is preferably used.

  The polyether ester amide is a block polymer having a polyoxyethylene chain as a hydrophilic segment, and can be obtained, for example, by the methods described in JP-A-49-8472 and JP-A-6-287547.

  A block polymer having a structure in which a polyolefin block and a block having a polyoxyethylene chain are alternately and repeatedly bonded can be obtained, for example, by the method described in JP-A-2001-278985. The polyoxyethylene chain functions as a hydrophilic segment, and exhibits antistatic performance by having a polyoxyethylene chain.

  A preferable blending amount of the antistatic agent (d) is 5 to 80% by mass, and more preferably 15 to 30% by mass. In the range of 5 to 80% by mass, a good antistatic effect is easily obtained. Moreover, by setting it as 15-30 mass%, while being able to obtain the stable antistatic effect, transparency is easy to be obtained at the time of thin-wall molding.

  For the purpose of further improving the antistatic property, an antistatic agent (e) other than the above-described antistatic agent (d) may be used in combination as necessary.

  Antistatic agent (e) includes surfactant (e1) [anionic surfactant (e11), cationic surfactant (e12), nonionic surfactant (e13), amphoteric surfactant (e14) and the like], Other salts (e2) other than the salt in (e1) and ionic liquid (e3) are included.

  Examples of the anionic surfactant (e11) include carboxylate, sulfate ester salt, sulfonate salt, phosphate ester salt, and a mixture of two or more thereof. These can be used individually by 1 type or in mixture of 2 or more types.

  The cation constituting the anionic surfactant (e11) is not particularly limited as long as it forms a salt, and examples thereof include alkali metals, alkaline earth metals, and ammonium.

  Examples of the carboxylate include salts of C8-20 higher fatty acids (octanoic acid, lauric acid, stearic acid, oleic acid, eicosanoic acid, etc.), but are not particularly limited thereto.

  Examples of the sulfate ester salt include sulfate ester salts of C8-20 higher alcohols (octyl alcohol, cetyl alcohol, lauryl alcohol, stearyl alcohol, eicosyl alcohol, etc.), higher alkyl ethers [ethylene oxides of the above higher alcohols (EO). ) (1-50 mol) adducts] sulfate salt, funnel oil, castor oil, sulfated oil (sulfated oil such as sulfated beef oil, sulfated peanut oil, sulfated Macquarie whale oil), sulfated fatty acid Examples thereof include salts of esters (sulfated butyl oleate, sulfated ricinoleate, etc.) and salts of C8-20 sulfated olefins, but are not particularly limited thereto.

  Examples of sulfonates include alkylbenzene sulfonates having C8-20 alkyl (octyl, lauryl, octadecyl, eicosyl, etc.) groups, C8-20 alkyl (above) sulfonates, C10-20 ( Alkyl) naphthalene (di) sulfonate (1-naphthalenesulfonate, 1,4-naphthalenedisulfonate, 2-methyl-1-naphthalenesulfonate, 2-methyl-1,4-naphthalenedisulfonate, etc. ), C8-20 α-olefin sulfonate, Igepon T-type sulfonate, C8-20 sulfosuccinate dialkyl ester (sodium di-2-ethylhexyl sulfosuccinate), polyvinyl sulfonate (Polystyrene sulfonic acid salts, etc.) It is not particularly limited.

  Examples of phosphoric acid ester salts include mono- and di-ester salts of C8-20 higher alcohols (above), but are not particularly limited thereto.

  Of these anionic surfactants (e11), from the viewpoint of antistatic properties, higher fatty acid salts, alkylbenzene sulfonates, alkyl sulfonates and mixtures thereof are preferred, and stearates and dodecylbenzene sulfonic acids are more preferred. Salts, lauryl sulfonates and mixtures thereof, more preferably sodium stearate, sodium dodecylbenzene sulfonate, sodium lauryl sulfonate and mixtures thereof.

Examples of the cationic surfactant (e12) include quaternary ammonium salts and / or phosphonium salts, and examples thereof include, but are not particularly limited to, compounds represented by the following formulae. A cationic surfactant (e12) can be used individually by 1 type or in mixture of 2 or more types.

In the formula, J is a nitrogen atom or phosphorus atom (preferably a nitrogen atom); R ⁷ and R ¹⁰ are C1-20 alkyl groups or C6-20 (substituted) phenyl groups; R ⁸ and R ⁹ are amides A C1-20 alkylene group or (substituted) phenylene group which may have a bond, an imide bond, an ester bond, an ether bond or a urea bond, and may be bonded to each other to form a ring; Anion; v is an integer of 1 to 10 (preferably 1 to 6).

  As an anion constituting the cationic surfactant (e12), heat loss starting temperature in air [JIS K7120 (1987), 8. The value measured according to the method for analyzing the TG curve described in the paragraph] is 200 ° C. or higher. For example, a super strong acid [a Hammett acidity function (−H0) is at least 12] conjugate base and And anions other than.

In the formula, when R ⁷ , R ⁸ , R ⁹ and R ¹⁰ do not have β hydrogen (for example, tetramethylammonium, trimethylbenzylammonium), Hofmann decomposition cannot occur. Any anion other than can be used, but when R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have β hydrogen (for example, trimethylethylammonium, didecyldimethylammonium), a conjugate base of a super strong acid is preferable.

  Examples of anions other than the conjugated base of super strong acid include halogen (fluorine, chlorine, bromine, etc.) ions, alkyl (C1-12) benzenesulfonic acid (p-toluenesulfonic acid, dodecylbenzenesulfonic acid, etc.) ions and poly ( n = 1-25) Fluoroalkanesulfonic acid (undecafluoropentanesulfonic acid, etc.) ions and the like, but are not particularly limited thereto.

  Examples of super strong acids include those derived from proton acids, combinations of proton acids and Lewis acids, and mixtures thereof.

  Examples of the protonic acid as the super strong acid include bis (trifluoromethylsulfonyl) imidic acid, bis (pentafluoroethylsulfonyl) imidic acid, tris (trifluoromethylsulfonyl) methane, perchloric acid, fluorosulfonic acid, alkane ( C1-30) sulfonic acid [methanesulfonic acid, dodecanesulfonic acid, etc.], poly (n = 1-30) fluoroalkane (C1-30) sulfonic acid (trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfone Acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid, etc.), borofluoric acid, tetrafluoroboric acid, and the like, but are not particularly limited thereto.

  Examples of proton acids used in combination with Lewis acids include hydrogen halides (hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, etc.), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethanesulfone. Examples include acid, pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid, and mixtures thereof, but are not particularly limited thereto.

  Examples of Lewis acids include fluorides of group IIIA elements (boron, thallium, etc.) (boron trifluoride, thallium pentafluoride, etc.) and fluorides of group VA elements (phosphorus, antimony, arsenic, etc.) (pentafluoride). Phosphorus, antimony pentafluoride, arsenic pentafluoride, etc.), fluorides of group VB elements (tantalum, etc.) (tantalum pentafluoride, etc.), and mixtures thereof are not particularly limited thereto. Of these, boron trifluoride and phosphorus pentafluoride are preferable from the viewpoint of antistatic properties.

  The combination of the protonic acid and the Lewis acid is arbitrary and is not particularly limited. Examples of super strong acids comprising a combination of a protonic acid and a Lewis acid include tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorothalamic acid, hexafluorotantalic acid, hexafluoroantimonic acid, and hexafluorothallium sulfonic acid. , Tantalum hexafluoride sulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, chloroboron trifluoride, arsenic hexafluoride and the like, but not limited thereto. These may be used alone or as a mixture of two or more.

  Among the anions constituting the cationic surfactant (e12), from the viewpoint of antistatic properties, a super strong acid conjugate base (a super strong acid consisting of a proton acid and a super strong acid conjugate base consisting of a combination of a proton acid and a Lewis acid) And more preferably, a super strong acid composed of a proton acid and a conjugate base of a super strong acid composed of a proton acid and boron trifluoride and / or phosphorus pentafluoride among Lewis acids.

  Hereinafter, specific examples of the quaternary ammonium salt in the cationic surfactant (e12) include (1) a salt with an anion other than a conjugate base of a super strong acid, and (2) a super strong acid (protonic acid, proton acid and Examples thereof are divided into salts with conjugate bases in combination with Lewis acids.

(1) Salts of super strong acids with anions other than conjugate bases Quaternary ammonium, for example, tetramethylammonium, tetraethylammonium, trimethylbenzylammonium, trimethyldodecylammonium, didecyldimethylammonium, trimethyl-2-ethylhexylammonium, etc. Examples include an anion other than a conjugate base of a super strong acid, for example, a salt combined with fluoride, chloride, bromide, p-toluenesulfonic acid, undecafluoropentanesulfonic acid and the like.

(2-1) Salt of super strong acid (protonic acid) with conjugate base Quaternary ammonium and super strong acid (protonic acid) conjugate base such as methanesulfonic acid, perchloric acid, fluorosulfonic acid, trifluoro Examples thereof include salts combined with romethanesulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, tridecafluorohexanesulfonic acid and the like.

(2-2) Salt of super strong acid (combination of proton acid and Lewis acid) with conjugated base Conjugated base of quaternary ammonium and super acid (combination of proton acid and Lewis acid) as described above, for example, tetrafluorobora Examples include salts in combination with acids, hexafluorophosphoric acid, hexafluorothalamic acid, hexafluoroantimonic acid, chloroboron trifluoride, hexafluorothallium sulfonic acid, and the like.

  Among the cationic surfactants (e12), specific examples of the phosphonium salt include (3) a salt of an anion other than a conjugate base of a super strong acid, and (4) a super strong acid (a combination of a proton acid, a proton acid and a Lewis acid). This is exemplified by dividing the salt with a conjugated base.

(3) Salt of super strong acid with anion other than conjugate base Phosphonium, for example, tetramethylphosphonium, tetraethylphosphonium, trimethylbenzylphosphonium, trimethyldodecylphosphonium, didecyldimethylphosphonium, trimethyl-2-ethylhexylphosphonium, etc. Examples include salts in combination with anions other than conjugated bases, such as fluoride, chloride, bromide, p-toluenesulfonic acid, undecafluoropentanesulfonic acid, and the like.

(4-1) Salt of super strong acid (protonic acid) with conjugate base The above-mentioned phosphonium and super strong acid (protonic acid) conjugate base, for example, methanesulfonic acid, perchloric acid, fluorosulfonic acid, trifluoromethanesulfonic acid , Salts obtained by combining pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, tridecafluorohexanesulfonic acid, and the like.

(4-2) Salt of super strong acid (combination of proton acid and Lewis acid) with conjugated base Conjugated base of phosphonium and super strong acid (combination of proton acid and Lewis acid) described above, for example, tetrafluoroboric acid, hexa Examples thereof include salts obtained by combining fluorophosphoric acid, hexafluorothalamic acid, hexafluoroantimonic acid, chloroboron trifluoride, hexafluorothallium sulfonic acid and the like.

  Among the above (1) to (4), from the viewpoint of antistatic properties, a super strong acid conjugate base (a super strong acid consisting of a proton acid and a super strong acid conjugate base consisting of a combination of a proton acid and a Lewis acid) is preferable. More preferably, it is a super strong acid composed of a proton acid and a conjugate base of a super strong acid composed of boron trifluoride and / or phosphorus pentafluoride among the proton acid and Lewis acid. These may be used alone or in a mixture of two or more, or may be a mixture of an anion other than a conjugate base of a super strong acid and a conjugate base of a super strong acid.

  In the case of a mixture of an anion other than a conjugate base of a super strong acid and a conjugate base of a super strong acid, the ratio (mass ratio) is preferably 95/5 to 5/95, more preferably from the viewpoint of antistatic properties. 70/30 to 30/70.

  Examples of the nonionic surfactant (e13) include polyethylene glycol type [ethylene oxide (EO) (1 to 50 mol) adduct of higher alcohol (same as above), higher fatty acid (same as above) EO (1 to 1). 30 mol) adduct, EO (1-50 mol) adduct of higher alkylamine (C8-18, such as 1-octylamine, 1-dodecylamine, etc.), EO of polypropylene glycol (Mn 1,000-3,000) (5-150 mol) adducts, etc.]; polyhydric alcohol type [polyethylene oxide (polymerization degree n = 3 to 300), fatty acid of glycerin (C4 to 30 such as caproic acid, octylic acid, lauric acid, stearic acid, olein) Acid etc.) esters, pentaerythritol fatty acids (above) esters, sorbitol or sorbitan Fatty acid (above) esters, polyhydric alcohols (C3-12, such as glycerin, sorbitan, etc.) alkyl (C1-30) ethers, alkanolamine (C2-20) fatty acids (above) amides, etc.] Is mentioned. These can be used individually by 1 type or in mixture of 2 or more types.

  Examples of the amphoteric surfactant (e14) include amino acid type [higher alkyl (C8-18) aminopropionate etc.], betaine type [higher alkyl (C8-18) dimethylbetaine, higher alkyl (C8-18) dihydroxy. Ethyl betaine, etc.]. These can be used individually by 1 type or in mixture of 2 or more types.

  Examples of the other salt (e2) include a salt of an alkali metal (lithium, sodium, potassium, etc.), an alkaline earth metal (magnesium, calcium, etc.) and a protonic acid. Here, examples of the protonic acid include those exemplified in combination with the aforementioned Lewis acid.

  Specific examples of other salts (e2) include, for example, fluorides (lithium fluoride, -sodium, -potassium, -magnesium, -calcium, etc.), chlorides (lithium chloride, -sodium, -potassium, -magnesium, -Calcium, etc.), bromides (lithium bromide, -sodium, -potassium, -magnesium, -calcium, etc.), iodides (lithium iodide, -sodium, -potassium, -magnesium, -calcium, etc.), perchlorates (Lithium perchlorate, -sodium, -potassium, -magnesium, -calcium, etc.), fluorinated sulfonates (lithium fluorosulfonate, -sodium, -potassium, -magnesium, -calcium, etc.), methanesulfonate ( Lithium methanesulfonate, -sodium, -potassium, -magnesium, Calcium), trifluoromethanesulfonate (lithium trifluoromethanesulfonate, -sodium, -potassium, -magnesium, -calcium, etc.), pentafluoroethanesulfonate (lithium pentafluoroethanesulfonate, -sodium, -potassium, -Magnesium, -calcium, etc.), nonafluorobutanesulfonate (lithium nonafluorobutanesulfonate, -sodium, -potassium, -magnesium, -calcium, etc.), undecafluoropentanesulfonate (undecafluoropentanesulfonate) Lithium, -sodium, -potassium, -magnesium, -calcium, etc.), tridecafluorohexanesulfonate (lithium tridecafluorohexanesulfonate, -sodium, -potassium, -ma Neshiumu, - calcium, etc.) and the like. Among these, from the viewpoint of antistatic properties, chlorides and perchlorates are preferable, and lithium chloride, potassium chloride, lithium perchlorate, potassium perchlorate, and sodium perchlorate are more preferable.

  The ionic liquid (e3) is a compound excluding the above-described surfactant (e1) and other salts (e2), has a melting point of room temperature or lower, and is a cation or anion constituting the ionic liquid (e3). Of these, at least one of them is an organic ion and has an initial conductivity of 1 to 200 ms / cm (preferably 10 to 200 ms / cm), for example, a room temperature molten salt described in WO95 / 15572. .

  Examples of the cation constituting the ionic liquid (e3) include an amidinium cation, a guanidinium cation, and a tertiary ammonium cation.

  Examples of the amidinium cation include imidazolinium cation [1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 1,3-dimethylimidazoli. Nium, 1,3-dimethyl-2,4-diethylimidazolinium, etc.], imidazolium cation [1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-ethyl-3-methylimidazolium, 1 , 2,3-trimethylimidazolium, etc.], tetrahydropyrimidinium cation [1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3-trimethyl-1,4,5, 6-tetrahydropyrimidinium, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium, 1,2 3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium and the like], and dihydropyrimidinium cation [1,3-dimethyl-1,4- or -1,6-dihydropyrimidinium, 1,2,3-trimethyl-1,4- or -1,6-dihydropyrimidinium, 1,2,3,4-tetramethyl-1,4- or -1,6-dihydropyrimidinium, etc.] However, it is not particularly limited to these.

  Examples of guanidinium cations include guanidinium cations having an imidazolinium skeleton [2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3,4-trimethylimidazolinium. 2-diethylamino-1,3-dimethyl-4-ethylimidazolinium, 2-dimethylamino-1-methyl-3,4-diethylimidazolinium, etc.], a guanidinium cation having an imidazolium skeleton [2- Dimethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3-dimethyl-4-ethylimidazolium, 2-dimethylamino-1- Methyl-3,4-diethylimidazolium etc.], tetrahydropyrimidi Guanidinium cation having a uranium skeleton [2-dimethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1,3,4-trimethyl-1,4 , 5,6-tetrahydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium, etc.], and guanidinium having a dihydropyrimidinium skeleton Cation [2-dimethylamino-1,3,4-trimethyl-1,4- or -1,6-dihydropyrimidinium, 2-diethylamino-1,3,4-trimethyl-1,4- or -1, 6-dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4- or -1,6-dihydropyrimidinium, etc. Etc. The but not particularly limited thereto.

  Examples of the tertiary ammonium cation include, but are not limited to, methyl dilauryl ammonium.

  The amidinium cation, guanidinium cation and tertiary ammonium cation can be used alone or in combination of two or more. Of these, from the viewpoint of initial conductivity, an amidinium cation is preferable, an imidazolium cation is more preferable, and a 1-ethyl-3-methylimidazolium cation is more preferable.

  In the ionic liquid (e3), examples of the organic acid or inorganic acid constituting the anion include the following.

  Examples of the organic acid include carboxylic acid, sulfate ester, higher alkyl ether sulfate ester, sulfonic acid, and phosphate ester.

  Examples of inorganic acids include super strong acids (for example, borofluoric acid, tetrafluoroboric acid, perchloric acid, hexafluorophosphoric acid, hexafluoroantimonic acid, hexafluoroarsenic acid), phosphoric acid and boric acid. Etc.

  The said organic acid and inorganic acid can be used individually by 1 type or in mixture of 2 or more types.

  Among the organic acids and inorganic acids, from the viewpoint of the initial conductivity of the ionic liquid (e3), a super strong acid whose Hammett acidity function (-H0) of the anion constituting the ionic liquid (e3) is 12 to 100 The acid which forms anions other than the conjugate base of this, the conjugate base of a super strong acid, and these mixtures are preferable.

  Examples of the anion other than the conjugate base of the super strong acid include halogen ions, alkyl (C1-12) benzenesulfonate ions, poly (n = 1-25) fluoroalkanesulfonate ions, and the like as described above. It is done.

  Examples of super strong acids include those derived from proton acids, combinations of proton acids and Lewis acids, and mixtures thereof, as described above.

  Examples of the protonic acid as the super strong acid include the same as described above. Of these, borofluoric acid, trifluoromethanesulfonic acid, and bis (pentafluoroethylsulfonyl) imidic acid are preferred from the viewpoint of ease of synthesis.

  Examples of the protonic acid used in combination with the Lewis acid include those described above. Among these, hydrogen fluoride is preferable from the viewpoint of the initial conductivity of the ionic liquid (e3).

  Examples of the Lewis acid include the same as described above. Among these, boron trifluoride and phosphorus pentafluoride are preferable from the viewpoint of the initial conductivity of the ionic liquid (e3).

  The combination of the protonic acid and the Lewis acid is arbitrary and is not particularly limited. Examples of the super strong acid composed of these combinations include the same as described above.

  Of the above anions, from the viewpoint of the initial conductivity of the ionic liquid (e3), a conjugate base of a super strong acid (a super strong acid composed of a proton acid and a super strong acid composed of a combination of a proton acid and a Lewis acid) is preferred, and more A super strong acid composed of a proton acid and a conjugate base of a super strong acid composed of a proton acid and boron trifluoride and / or phosphorus pentafluoride are preferred.

  As a method for producing the ionic liquid (e3), for example, a dimethyl carbonate salt of an amidinium cation and / or a guanidinium cation obtained by quaternization with dimethyl carbonate or the like is converted into an acid [in the ionic liquid (e3). The above-mentioned organic acid or inorganic acid constituting an anion] is added to carry out acid exchange, the amidinium cation and / or guanidinium cation is once hydrolyzed to form a monoamidoamine, and then the monoamidoamine is converted into an acid. And a method of neutralizing with the same as the organic acid or inorganic acid.

  The blending amount of the antistatic agent (e) is preferably 0.001 to 5% by mass, more preferably 0.01 to 3% by mass with respect to the total amount of the antistatic resin composition from the viewpoint of resin physical properties. %.

  The method of adding the antistatic agent (e) is not particularly limited. For example, the method of adding (e) to (d) in advance, (a) to (d) and (e) are mixed together, Alternatively, after mixing with one component selected from (a) to (c), and again mixing with a plurality of or one component selected from the remaining (a) to (d), or (a) After mixing with a plurality of components selected from-(d), it can be optionally carried out, for example, by mixing again with a plurality or one component selected from the remaining (a)-(d). From the viewpoint of effective dispersion in the antistatic resin composition, a method of dispersing in advance in (d) is preferable, and in particular, during the production of (d) [in the raw material of (d), (d) In the middle of the production and / or after the production of (d), a method in which (e) is previously added and dispersed is preferred.

  The antistatic resin composition may contain any additive depending on various purposes. The type of additive is not particularly limited, and includes, for example, inorganic fillers, pigments such as iron oxide, stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bisstearamide, lubricants, and the like. Molding agents, paraffinic process oils, naphthenic process oils, aromatic process oils, paraffins, organic polysiloxanes, mineral oils and other softeners / plasticizers, hindered phenolic antioxidants, phosphorus heat stabilizers, etc. Antioxidants, hindered amine light stabilizers, benzotriazole ultraviolet absorbers, flame retardants, organic fibers, glass fibers, carbon fibers, metal whiskers and other reinforcing agents, colorants, other additives or mixtures thereof, resins, Examples of those generally used for blending rubbery polymers include, but are not limited to these. No. These can be used individually by 1 type or in mixture of 2 or more types.

  The antistatic resin composition preferably contains a hydrogenated product of a styrene-butadiene block copolymer. The hydrogenated styrene-butadiene block copolymer includes a polymer block C mainly composed of at least one vinyl aromatic hydrocarbon and a polymer block D mainly composed of at least one conjugated diene, A block copolymer in which 80% or more of the conjugated diene moiety is hydrogenated. The hydrogenated styrene-butadiene block copolymer is preferably contained in an amount of 3 to 30 parts by mass with respect to 100 parts by mass of the resin composition comprising (a), (b), (c) and (d).

  The hydrogenated product of the styrene-butadiene block copolymer can be obtained by hydrogenating the conjugated diene portion of the obtained copolymer in the same manner as the block copolymer (a).

  The hydrogenation catalyst for obtaining a hydrogenated product of a styrene-butadiene block copolymer is not particularly limited, and for example, the following hydrogenation catalysts known in the art can be used.

  (A) A supported heterogeneous hydrogenation catalyst in which a metal such as NI, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like (i) NI, Co, Fe, Cr, etc. So-called organometals such as so-called Ziegler-type hydrogenation catalysts using transition metal salts such as organic acid salts or acetylacetone salts and reducing agents such as organoaluminum, and (c) organometallic compounds such as TI, Ru, Rh and Zr Examples of homogeneous hydrogenation catalysts such as complexes and specific hydrogenation catalysts include, for example, JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, and JP-B-1-39970. Examples described in Japanese Patent Publication No. 1-53851 and Japanese Patent Publication No. 2-9041.

  Preferable hydrogenation catalysts include, for example, titanocene compounds and / or mixtures of titanocene compounds and reducing organometallic compounds, but are not particularly limited thereto.

  Examples of the titanocene compound include compounds described in JP-A-8-109219. More specifically, for example, at least a ligand having a (substituted) cyclopentadienyl skeleton, indenyl skeleton or fluorenyl skeleton such as biscyclopentadienyl titanium dichloride, monopentamethylcyclopentadienyl titanium trichloride, etc. Although the compound etc. which have 1 or more are mentioned, it is not specifically limited to these.

  Examples of the reducing organometallic compound include, but are not limited to, organic alkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.

  Here, the hydrogenation reaction is generally performed in a temperature range of 0 to 200 ° C, more preferably 30 to 150 ° C. Moreover, the pressure of hydrogen used for the hydrogenation reaction is usually 0.1 to 15 MPa, preferably 0.2 to 10 MPa, and more preferably 0.3 to 7 MPa. Furthermore, the hydrogenation reaction time is usually 3 minutes to 10 hours, preferably 10 minutes to 5 hours.

  The hydrogenation reaction can be performed by any of a batch process, a continuous process, or a combination thereof. Further, the hydrogenation rate can be known by a nuclear magnetic resonance apparatus (NMR).

  In the block copolymer (b), the hydrogenation rate of the unsaturated double bond based on the conjugated diene is preferably 40% or more. When the hydrogenation rate is 40% or more, a stable antistatic effect is easily obtained, and the transparency during thin-wall molding tends to be better.

  When a hydrogenated styrene-butadiene block copolymer is used, the content of the vinyl aromatic hydrocarbon polymer component in the hydrogenated product is determined by the oxidative decomposition of the block copolymer before hydrogenation. You can figure out how to do it.

  Further, the microstructure (ratio of cis, trans, vinyl) of the conjugated diene portion of the hydrogenated product of the styrene-butadiene block copolymer is not particularly limited. The ratio of cis, trans, and vinyl can be arbitrarily changed by using the aforementioned polar compound or the like.

  Generally, the vinyl bond content is preferably in the range of 5 to 90%, more preferably 10 to 80%, and still more preferably 15 to 75%. In this specification, the amount of vinyl bonds means the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (however, when 1,3-butadiene is used as the conjugated diene, -Vinyl bond amount). This vinyl bond amount can be grasped by a nuclear magnetic resonance apparatus (NMR).

  The addition amount of the hydrogenated styrene-butadiene block copolymer is preferably 3 to 30% by mass, more preferably 5 to 20% by mass, based on the total amount of the antistatic resin composition. Within this range, a stable antistatic effect and good transparency at the time of thin-wall molding tend to be easily obtained.

  The antistatic resin composition preferably contains an acid anhydride group-modified product of a styrene-butadiene block copolymer. An acid anhydride group-modified product of a styrene-butadiene block copolymer comprises at least one polymer block C mainly composed of vinyl aromatic hydrocarbon and polymer block D mainly composed of at least one conjugated diene. It is a block copolymer containing. The acid anhydride group-modified product of the styrene-butadiene block copolymer is contained in an amount of 3 to 30 parts by mass with respect to 100 parts by mass of the resin composition comprising (a), (b), (c) and (d). Is preferred.

  The acid anhydride group-modified product of the styrene-butadiene block copolymer was prepared by combining the obtained copolymer and the acid anhydride group-containing compound in the presence of a peroxide compound in the same manner as the block copolymer (a). For example, a resin composition prepared by a kneader such as a kneader, a Banbury mixer, or a roll, a mixer such as a ribbon blender or a Henschel mixer is supplied to a single or twin screw extruder, and is obtained by heating and melt-kneading. Can do.

  Examples of the acid anhydride group-containing compound include maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, aconitic anhydride, and hymic acid anhydride, but are not particularly limited thereto. Of these, maleic anhydride is preferred.

In addition, the addition amount of the acid anhydride group to the styrene-butadiene block copolymer is determined by a calibration curve method based on the absorption derived from the acid anhydride group near 1790 cm ⁻¹ by, for example, infrared spectroscopy. Can do. More specifically, after a styrene-butadiene block copolymer and a predetermined amount of maleic anhydride are made into a chloroform solution, a film is prepared by a cast method, and a calibration curve is prepared from infrared absorbance, whereby an acid anhydride group is prepared. Can be obtained.

  In the present specification, an acid anhydride group-modified product of a styrene-butadiene block copolymer produced using an extruder was used as a toluene solution, and then obtained by precipitation filtration with 5 times the amount of methanol with respect to toluene. After the solid was dried, a film was prepared by the casting method, the infrared absorbance was measured, and the amount of maleic anhydride added was determined from the calibration curve.

  A preferable addition amount of the acid anhydride group is 0.5 to 5% by mass. In the range of 0.5 to 5% by mass, the color of the antistatic resin composition and its molded product tends not to be impaired.

  The addition amount of the acid anhydride group modified product of the styrene-butadiene block copolymer is 100 parts by mass of the antistatic resin composition comprising the component (a), the component (b), the component (c), and the component (d). On the other hand, it is preferable that it is 3-30 mass parts. Within this range, a stable antistatic effect and good transparency at the time of thin-wall molding tend to be easily obtained.

  The antistatic resin composition is molded by a known method generally used for molding a thermoplastic resin, for example, injection molding, extrusion molding, blow molding, vacuum molding, inflation molding, film molding, sheet molding, or the like. be able to. The shape of the antistatic resin molded body is not particularly limited, and may be, for example, a film shape or a sheet shape.

  The antistatic resin laminate can be obtained by forming a surface layer made of an antistatic resin composition on one surface of a base material layer made of a thermoplastic resin. The method for forming the surface layer made of the antistatic resin composition on one side of the base layer of the thermoplastic resin is not particularly limited, and is a method used for general multilayer molding, for example, two-color molding method in injection molding, multilayer Examples thereof include a method using a T die, a method in which a surface film or sheet is prepared in advance and bonded or heat-sealed, and a method of bonding via an adhesive layer. By forming the surface layer made of the antistatic resin composition in this manner, antistatic properties can be imparted, and for example, scraping is less likely to occur when rubbing against the product during product transportation. Therefore, it can be suitably used as a container / transport container for optical parts such as lens parts and display panels, and electronic parts such as IC chips.

  In the antistatic resin laminate having the surface layer made of the antistatic resin composition on one side of the base material layer made of the thermoplastic resin, the thickness of the surface layer is preferably 5 μm to 0.2 mm. Within this range, it tends to be easy to obtain a product having excellent transparency.

  The method for obtaining the antistatic resin laminate having a surface layer thickness of 5 μm to 0.2 mm is not particularly limited. For example, a method of making a multilayer sheet having a desired surface thickness using a T-die extruder, a multilayer sheet having a surface layer exceeding the desired thickness or 0.2 mm by a T-die extruder, etc. A method of adjusting the thickness of the surface layer to 5 μm to 0.2 mm by drawing using a drawing device such as a drawing machine, after creating a thin film in advance by inflation molding or a stretcher, etc. And a method of bonding to a thermoplastic resin.

  Antistatic resin moldings and antistatic resin laminates are available for pressure forming (extrusion pressure forming, hot plate pressure forming, vacuum pressure forming, etc.), free blow molding, vacuum forming, bending, match mold forming, heat By a conventional technique such as plate molding, it can be easily molded into a secondary molded product.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

Evaluation methods used in Examples and Comparative Examples are as follows.
(A) Evaluation (a) Block ratio Method of oxidatively decomposing a block copolymer with di-tertiary butyl hydroperoxide using osmium tetroxide as a catalyst [I. M.M. KOLTHOFF, et al. , J .; Polym. Sci. 1,429 (1946)] was quantified and determined from the following formula.
Vinyl aromatic of block copolymer
Mass% of hydrocarbon polymer block
Block ratio (mass%) = ――――――――――――――――― × 100
All vinyl block copolymer
% By mass of aromatic hydrocarbon

(B) Styrene content The styrene content was measured using an ultraviolet spectrophotometer (device name: UV-2450; Shimadzu Corporation).

(C) Hydrogenation rate The hydrogenation rate was measured with a nuclear magnetic resonance apparatus (device name: DPX-400; manufactured by BRUKER, Germany).

(D) Surface resistance value The surface resistance value is calculated according to SIMCO JAPAN. It measured using the surface resistance measuring device (TRUSTAT ST-3) made from INC.

(E) Grinding test Vertically and horizontally 14mm × 20mm, 64pin IC chip, leaving only the four corner pins on the flat plate sample, this was subjected to vertical vibration using a sieve shaker (Fritsch, SPARTAN). Then, after oscillating for 2 hours, the state of shavings adhering to the pin was observed using a laser microscope.
Pins with no scraps attached to the pins were marked with ◯, and those with sticks attached were marked with ×.

(F) Tensile strength Based on ASTM D638, MD was measured at a test speed of 5 mm / min using a TG-5KN type tester manufactured by Minebea Co., Ltd.

(G) Vicat softening temperature Based on ISO306, it measured using the load 10N and the temperature increase rate of 50 K / h using Toyo Seiki Co., Ltd. HDT-TESTER ST-3.

(H) Bending resistance test In accordance with JIS P8115-2001, the number of bendings to breakage was measured in the sheet extrusion direction (MD) under the conditions of a load of 1.0 kgf and a bending angle of 135 ° C.

(I) Total light transmittance Based on JIS K7105, Nippon Denshoku Co., Ltd. haze meter (1001DP) was used. The measurement was performed by applying liquid paraffin.

(J) Stretching thin film property After forming a 0.2 mm sheet by thickness press molding, it was stretched 6 times in a uniaxial direction at 140 ° C. using a stretcher (manufactured by Toyo Seiki Co., Ltd.). .
Of the 10 stretched films, 10 films were able to be produced. Samples with the sheet ruptured at the chuck site due to the stress during stretching are: one that breaks 1 to 3 of 10 sheets, △ that breaks 3 to 5 sheets, and one that breaks 6 or more sheets X.

(K) Blocking property 5 sheets of 10 cm length and 5 cm width were stacked, and after applying a pressure of 100 g / cm ² at 40 ° C. for 7 days, the sheet was peeled off. Evaluations were made with 5 points for peeling off, 4 points for low resistance, 3 points for resistance, 2 points for tearing when peeling, and 1 point for non-peeling.

(B) Raw materials used (1) Block copolymer (a-1)
Using an autoclave equipped with a stirrer, under a nitrogen gas atmosphere, i) 0.080 parts by mass of n-butyllithium was added to a cyclohexane solution containing 25 parts by mass of styrene and polymerized at 80 ° C. for 20 minutes.
Next, ii) A cyclohexane solution containing 3 parts by mass of styrene and 30 parts by mass of 1,3-butadiene was continuously added for 60 minutes to polymerize at 80 ° C.
Next, iii) A cyclohexane solution containing 42 parts by mass of styrene was continuously added for 25 minutes to polymerize at 80 ° C., and then kept at 80 ° C. for 10 minutes. Thereafter, the polymerization was stopped by adding methanol to the polymerization vessel at a 0.9-fold molar ratio with respect to n-butyllithium, and 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) as a stabilizer ) Ethyl] -4,6-di-t-pentylphenyl acrylate is added to 0.5 part by mass with respect to 100 parts by mass of the block copolymer, and then the solvent is removed to obtain the block copolymer (a-1). Obtained.
The obtained block copolymer (a-1) was polymer block A in which styrene / 1,3-butadiene = 100/0 mass ratio, and styrene / 1,3-butadiene = 9/91 mass ratio. It is an ABA block polymer composed of a polymer block A in which the combined block B and styrene / 1,3-butadiene = 100/0 mass ratio. This block copolymer (a-1) had a number average molecular weight of 85,000, a styrene content of 70% by mass, and a block rate of 95% by mass. The melt flow rate was 7 g / 10 min (according to ASTM D1238, 200 ° C., load 5 kg).

(2) Block copolymer (a-2 to a-8, b-B-1)
Using the same method as the block copolymer (a-1), the amount of styrene and 1,3-butadiene added in i), ii) and iii) of (a-1), and n-butyllithium The block copolymer (a-2 to a-8, b-B-1) was produced by appropriately controlling the amount of addition. In addition, if the amount of styrene added in ii) is increased with respect to the amount of styrene added in i) and iii), the styrene block rate decreases.

(3) Polystyrene resin Polystyrene: HF77 (manufactured by PS Japan, MI = 7.7 g / 10 min)
Styrene methyl methacrylate resin: Ethylene MS200 (manufactured by Nippon Steel Chemical Co., Ltd., MI = 1.6 g / 10 min)
Block copolymer: b-B-1
Was used as a polystyrene resin.

(4) Impact-resistant polystyrene resin (HIPS)
Among commercially available HIPS, HIPS having an average rubber particle diameter of 2.8 μm and a rubber amount of 7.0% was used as (c-1).

(5) Antistatic material d-1 (polyether ester amide): Polynox MB-67 (manufactured by Nano Chem Tech)
d-2 (a block polymer having a structure in which a block of polyolefin and a block having a polyoxyethylene chain are alternately and repeatedly bonded): Pelestat HC250 (manufactured by Sanyo Chemical Co., Ltd.)
Was used as an antistatic agent.

(7) Hydrogenated styrene-butadiene block copolymer As a hydrogenation catalyst, 1 liter of dried and purified cyclohexane was charged into a nitrogen-substituted reaction vessel, and 100 mmol of bis (η5-cyclopentadienyl) titanium dichloride was added. Then, an n-hexane solution containing 200 mmol of trimethylaluminum was added with sufficient stirring, and reacted at room temperature for about 3 days to prepare a hydrogenation catalyst.
The hydrogenation catalyst thus obtained was added at 100 ppm as titanium per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C.
Thereafter, methanol was added, and then 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by mass of the block copolymer. Thereafter, the solvent was removed to obtain a hydrogenated block copolymer.
The hydrogenation rate of the block copolymer hydrogenated product was adjusted by the amount of hydrogen so that the hydrogenation rate was 50%.
A block copolymer before hydrogenation was prepared in the same manner as the method shown for the block copolymer (a-1) and then subjected to hydrogenation reaction. (F-1) 65% by mass of styrene and 35% by mass of butadiene A hydrogenated product of a block copolymer consisting of

(8) Acid anhydride group modified product of styrene-butadiene block copolymer Toughprene 126 (manufactured by Asahi Kasei Chemicals Co., Ltd.) and maleic anhydride at a ratio of 95/5 mass% (manufactured by Ikekai Co., Ltd., PCM-30) was extruded at 180 ° C. to obtain an acid anhydride group-modified product of a styrene-butadiene block copolymer having a maleic anhydride addition amount of 3% by mass.

(9) ABS resin ABS191 (Asahi Kasei Chemicals Corporation) was used.

[ Reference Examples 1 to 6 and Comparative Examples 1 to 4]
Each raw material pellet was charged according to the formulation shown in Table 3 into a hopper of a union plastics T-die mounting extruder (USV type / barrel diameter 40 mmφ, L / D = 28, width 400 mm T-die mounting). The temperature of the resin in the cylinder of the extruder and the temperature of the T die were adjusted, and a sheet having a thickness of about 0.3 mm was extruded.
About the obtained sheet | seat, based on the method described in the item of (evaluation), the surface resistance value, the shaving test, the tensile strength, and the Vicat softening temperature were measured. Table 3 shows the results.

[ Reference Examples 7-9, Examples 10-12 , Comparative Examples 5-7]
After using the Ikegai biaxial extruder (PCM30) to produce pellets with the formulation shown in Table 4, as in Reference Example 1 , a sheet with a thickness of 0.3 mm and a thickness of 0.2 mm The sheet was extruded.
About the obtained sheet | seat of thickness 0.3mm, the surface resistance value, the cutting test, the bending resistance, and the blocking property were measured. Table 4 shows the results.
In addition, a film having a thickness of 10 μm (surface layer) was prepared from the obtained sheet having a thickness of 0.3 mm using a press molding machine, and a plate (base material) having a thickness of 2 mm using the copolymer a-2. Layer) was prepared in advance by a press molding machine. The 10 μm-thick film (surface layer) was placed on this 2 mm-thick plate (base material layer) and bonded together under a load of 200 ° C. and 5 kg / cm 2, and then the total light transmittance was measured.
Further, the stretched thin film forming property was evaluated on the sheet having a thickness of 0.2 mm based on the method described in the section of the evaluation method.

  The antistatic resin composition, the antistatic resin molded body, and the antistatic resin laminate of the present invention have good antistatic properties, and the scraps do not adhere to the product when they are rubbed with the product. Therefore, it can be used widely and effectively in applications that dislike static electricity and dust adhesion, particularly in containers for transporting optical components and electrical / electronic components. In addition, since the moldability of the thin film is good and the transparency of the thin film is excellent, by laminating on the resin surface layer, it is possible to provide a molded body excellent in antistatic properties, dust adhesion prevention, and transparency. It can be used widely and effectively in containers and the like that require transparency, such as carrier tape.

Claims (8)

It comprises at least one polymer block A mainly composed of vinyl aromatic hydrocarbons and at least one polymer block B mainly composed of conjugated dienes, and has a vinyl aromatic hydrocarbon content of 60 to 95% by mass. At least one block copolymer (a), a styrene resin (b), an impact-resistant polystyrene resin (c) having an average particle diameter of rubber particles of 0.5 to 5 μm, and a polyoxyethylene chain The antistatic agent (d) is contained, and the content of these (a), (b), (c), and (d) is (a) / (b) / (c) / (d) = 20 to 90 wt% / 0-70 mass% / 0-20 mass% / 5 to 80% by mass is, furthermore, a styrene - butadiene block copolymer hydrogenated products, and / or styrene - butadiene block copolymer The acid anhydride group-modified product is the above (a), ( ), And wherein the Rukoto contains 3 to 30 parts by weight per 100 parts by weight resin composition comprising (c) and (d),
Antistatic resin composition. In the block copolymer (a), the proportion of the vinyl aromatic hydrocarbon polymer block is 60% by mass or more of the total vinyl aromatic hydrocarbon in the block copolymer.
The antistatic resin composition according to claim 1. The styrenic resin (b) comprises at least one polymer block C composed of vinyl aromatic hydrocarbons and at least one copolymer block D mainly composed of vinyl aromatic hydrocarbons. It is at least one block copolymer component (b-B) having a hydrocarbon content of 60 to 95% by mass,
The antistatic resin composition according to claim 1 or 2. The antistatic agent (d) is a polyether ester amide.
The antistatic resin composition as described in any one of Claims 1-3. The antistatic agent (d) is a block polymer having a structure in which a block of polyolefin and a block having a polyoxyethylene chain are repeatedly bonded alternately.
The antistatic resin composition as described in any one of Claims 1-3. The antistatic resin composition according to any one of claims 1 to 5 ,
Antistatic resin molding. A base material layer made of a thermoplastic resin (B), a surface layer made of the antistatic resin composition (A) according to any one of claims 1 to 5 formed on one side of the base material layer, and It is characterized by having
Antistatic resin laminate. The thickness of the surface layer (A) is 5 μm to 0.2 mm.
The antistatic resin laminate according to claim 7 .