WO2004035685A1 - Composition de resine possedant d'excellentes proprietes antistatiques, de durete de surface et de resistance - Google Patents

Composition de resine possedant d'excellentes proprietes antistatiques, de durete de surface et de resistance Download PDF

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Publication number
WO2004035685A1
WO2004035685A1 PCT/JP2003/013268 JP0313268W WO2004035685A1 WO 2004035685 A1 WO2004035685 A1 WO 2004035685A1 JP 0313268 W JP0313268 W JP 0313268W WO 2004035685 A1 WO2004035685 A1 WO 2004035685A1
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Prior art keywords
resin
resin composition
thermoplastic elastomer
weight
styrene
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PCT/JP2003/013268
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English (en)
Japanese (ja)
Inventor
Ryuji Kamoshita
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Ps Japan Corporation
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Application filed by Ps Japan Corporation filed Critical Ps Japan Corporation
Priority to JP2004544973A priority Critical patent/JPWO2004035685A1/ja
Priority to KR1020047009318A priority patent/KR100589069B1/ko
Priority to AU2003273029A priority patent/AU2003273029A1/en
Publication of WO2004035685A1 publication Critical patent/WO2004035685A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof

Definitions

  • Resin composition with excellent antistatic properties, surface hardness and strength
  • the present invention relates to a resin composition obtained by imparting an antistatic property to a resin that is originally insulating, and has a superior antistatic property, excellent surface hardness and excellent strength that cannot be achieved by a conventional resin composition. Brightness related to the combined resin composition.
  • the resin composition of the present invention is preferably used as a material for transporting electronic components and the like, which plays a role of protecting the contents electrically and physically, and especially for a material for transporting electronic components which is repeatedly washed and used repeatedly. .
  • Synthetic resins are used in many industrial fields, taking advantage of their ease of molding, free coloring, and light weight. On the other hand, synthetic resin cannot be used due to its insulating properties! / There are industrial fields.
  • Techniques for imparting antistatic properties to synthetic resins include (i) a method of adding anion, cationic or nonionic surfactant as an antistatic agent, and (ii) addition of force pump rack or carbon fiber as a conductive filler. (Iii) There is also a technique of applying an antistatic agent or printing with a conductive ink to impart antistatic properties to the resin molded product.
  • the method (i) is based on the principle that the antistatic agent having poor compatibility with the synthetic resin bleeds out, so that the amount of the antistatic agent added is limited and the antistatic property is not stable. .
  • the technique (iii) since a large amount of black conductive filler is added, the freedom of coloring is lost.
  • the technique (iii) has a problem that coating and printing are required as an additional step, and that antistatic properties are lost due to surface friction during washing and use.
  • conventional techniques for imparting antistatic properties to synthetic resins include polyetheresteramides derived from poly (alkylene oxide) glycol, a carboxy group-containing vinyl polymer, and a styrene resin.
  • a resin composition is known (for example, Japanese Patent Application Laid-Open No. 60-23435). This is a polyetherester containing hydrophilic poly (alkylene oxide) glycol as an antistatic agent.
  • an antistatic resin composition comprising a rubber-reinforced styrene resin modified with a carboxyl group or an acid anhydride group, a polyethylene oxide block copolymer, and a metal salt which forms a solid solution with the styrene resin is known. It is known (for example, Japanese Patent Application Laid-Open No. H03-310346). This relates to a technology utilizing a polymer solid electrolyte formed of a polyethylene oxide structure and a metal salt. Examples of the metal salt include lithium salt, lithium nitrate, lithium bromide along with sodium salt and potassium salt. Lithium salts such as lithium borohydride, lithium iodide, and lithium perchlorate are exemplified. Japanese Patent Application Laid-Open No. H03-130346 discloses a lithium salt having a specific structure.
  • H03-130346 discloses that a polyethylene oxide-based block copolymer and a metal salt are used as a common solvent in order to produce a resin composition using a metal salt having a strong deliquescent property. It refers to a method of preparing a solid solution by dissolving the solvent after dissolving it in a liquid. However, it is easy and safe to dissolve the lithium salt of a specific structure in a chemical liquid of a specific structure at a specific concentration to make the resin composition easy and safe. There is no mention or suggestion that the product can be manufactured.
  • bis (trifluoromethanesulfonyl) imidlithium and a plasticizer selected from phthalates, aliphatic dibasic esters and glycol esters are used as a resin in a resin composition.
  • a transparent antistatic resin composition obtained by adding a resin (see, for example, JP-A-09-227743). This is specific To a technique for adding together type lithium salt and specific type of plasticizer, very Ri by the addition of relatively large amounts of lithium salts using a large amount of plasticizer 1 0 1 0 ⁇ .
  • an antistatic resin composition comprising a styrene-based polymer, polyethylene oxide of a specific molecular weight, a lithium salt and Darcol is known (for example, see JP-A-06-25666). No. 10 publication).
  • This relates to the technology of obtaining excellent antistatic properties by the synergistic action of polyethylene oxide, lithium salt and glycol, but the styrene polymer and polyethylene oxide are finely divided even when melted and kneaded. Since the resin composition does not disperse, the balance between the rigidity and impact resistance of the resin composition is poor, and further, since the glycol greatly reduces the heat resistance of the resin composition, the application as a molding material is limited.
  • polystyrene-based resins such as polystyrene and ABS resin, thermoplastic elastomers having polar organic groups, alkali or alkaline earth metal salts, alkylene oxide compounds in which all molecular chain terminals are alkyl, scaly
  • an antistatic resin composition comprising a fibrous inorganic filler is known (for example, International Publication No. WO 01/793454 pamphlet). This provides excellent antistatic properties due to the synergistic action of the thermoplastic elastomer, metal salt, and alkylene oxide compound of a specific structure, while giving excellent strength to inorganic filler of a specific structure. This is the technology that we are trying to do.
  • the heat resistance of the resin composition is greatly reduced when the alkylene oxide compound is added.
  • the addition of the inorganic filler improves the rigidity lost by the thermoplastic elastomer, but at the same time greatly reduces the impact resistance. Therefore, even if it can be applied to the resin composition using the original high heat resistance and high impact resistance ABS resin, rubber strength with relatively low heat resistance and low impact resistance Practical use is difficult for a resin composition using a functionalized polystyrene resin.
  • this resin composition has a low surface hardness, and there is a problem that the surface of a molded article is scraped off due to friction during washing or use. Furthermore, since the inorganic filler has a large specific gravity, this resin composition has lost the lightness, which is an advantage of the polystyrene resin.
  • the present inventor has found that a rubber-reinforced styrene resin, a thermoplastic elastomer having a specific composition, a lithium salt having a specific structure, and a styrene resin having a specific composition are blended in a specific amount, melted, the resin composition obtained by kneading ⁇ Pi granulation, 1 0 1 0 ⁇ / low surface resistivity of less than mouth and 1 0 1 0 ⁇ . cm below a low volume resistivity, withstand long-term-repeated use
  • the present inventors have found that they have a high balance between high surface hardness, high impact resistance and high rigidity, and arrived at the present invention.
  • the present inventor can dissolve, mix, knead, and granulate the lithium salt having the specific structure at a specific concentration in the chemical liquid having the specific structure more easily and safely.
  • the present inventors have found that excellent antistatic properties, excellent surface hardness, and excellent strength, which are not inferior to those of the above resin composition, can be obtained, and have reached the present invention.
  • the present invention relates to a rubber-reinforced styrene resin (A), a thermoplastic elastomer having a polyether block as a soft segment (B), and a formula (1)
  • Z represents a trifluoromethanesulfonyl group
  • n represents an integer of 1 to 3
  • the present invention provides a solution (Cs) in which the lithium salt (C) represented by the above formula (1) is dissolved in a chemical liquid represented by the following (2) at a concentration of 10 to 70% by weight.
  • the present invention also relates to the above resin composition blended in the form of
  • X represents hydrogen, an alkyl group having 1 to 4 carbon atoms, an acetate residue, a phthalate ester residue or an adipic ester residue
  • W represents a hydrogen or methyl group
  • m represents 1 to 9
  • V represents hydrogen or an alkyl group having 1 to 4 carbon atoms
  • the rubber-reinforced styrene resin (A), thermoplastic elastomer (B), lithium salt (C), and styrene resin (D) of the present invention are blended, melted, kneaded, and granulated in specific amounts.
  • A rubber-reinforced styrene resin
  • B thermoplastic elastomer having a polyether block as a soft segment
  • a formula (1) [Z ] n Y— L i + where Z represents a trifluoromethanesulfonyl group
  • the rubber-reinforced styrenic resin (A) is responsible for the properties such as moldability, colorability, and lightness of the resin composition of the present invention. Metharyl styrene copolymer resin and the like.
  • a rubber-reinforced polystyrene resin (hereinafter referred to as HIPS) is a molding material in which a rubber-like elastic material is dispersed in a particle form in a continuous phase composed of a polymer of styrene alone. Can be selected and used. Commonly available HIPS include styrene, degree of polymerization, type and amount of rubber-like elastic material, and dispersion particle size, and amount of plasticizer and lubricant, and fluidity, impact strength, elastic modulus and thermal deformation Different temperatures are provided.
  • HIPS HIPS with favorable flowability, impact strength, elastic modulus and heat distortion temperature are not available, use polystyrene resin (hereinafter referred to as GPPS) or styrene'butadiene block copolymer (hereinafter referred to as SB elastomer).
  • GPPS polystyrene resin
  • SB elastomer styrene'butadiene block copolymer
  • the fluidity, impact strength, modulus of elasticity and heat distortion temperature can be adjusted favorably.
  • a rubber-reinforced metharyl styrene copolymer resin hereinafter referred to as transparent HIPS is a continuous phase composed of a copolymer of methyl methacrylate, alkyl (meth) phthalate and styrene, and has a refractive index that matches that of the continuous phase.
  • Generally available transparent HIPS include the amount of methyl methacrylate, the type and amount of alkyl (meth) acrylate, the degree of polymerization of them with styrene, the type, amount and dispersion particle size of the rubber-like elastic material, the plasticizer and The amount of lubricant is adjusted and different transparency, flowability, impact strength, elastic modulus and heat distortion temperature are provided.
  • metharyl styrene copolymer resin hereinafter referred to as MS resin
  • SB elastomer is blended with transparent HIPS. Fluidity, impact strength, modulus of elasticity and heat distortion temperature can also be preferably adjusted.
  • the fluidity of the rubber-reinforced styrene resin (A) is preferably such that the melt flow rate measured according to ISOl 133 is in the range of 1 to 8 g / 1 Omin.
  • the following thermoplastic elastomer (B) and the following lithium salt solution (C s) significantly increase the fluidity of the resin composition, so that the fluidity of the rubber-reinforced styrene resin (A) is as described above. If the ratio is out of the range, the moldability of the resin composition of the present invention, particularly the extrusion moldability, is unpreferably decreased.
  • the impact strength of rubber-reinforced styrenic resin (A) conforms to ISO 179.
  • the measured Charpy impact strength is 5 kj Zm 2 or more.
  • the following thermoplastic elastomer (B) and the following styrene resin (D) affect the impact strength of the resin composition. If the impact strength of the rubber reinforced styrene resin (A) is within the above range, However, the resin composition of the present invention preferably has practical strength.
  • the elastic modulus of the rubber-reinforced styrene resin (A) is preferably at least 220 MPa.
  • thermoplastic elastomers (B) and the following styrenic resins (D) affect the elastic modulus of the resin composition, but the elastic modulus of the rubber-reinforced styrenic resin (A) falls within the above range.
  • the resin composition of the present invention has practical strength and is therefore preferable.
  • the thermal deformation temperature of the rubber-reinforced styrene-based resin (A) is preferably such that the Vicat softening temperature measured according to ISO306 is 85 ° C. or higher.
  • thermoplastic elastomer (B) and the following lithium salt solution (C s) significantly lower the heat distortion temperature of the resin composition
  • the heat distortion temperature of the rubber-reinforced styrene resin (A) is If the ratio is out of the range, the practical temperature of the resin composition of the present invention, for example, transportation in a hold is restricted, which is not preferable.
  • Thermoplastic 1 "raw elastomer one of the polyether block as a soft segment (B), when combined with the lithium salt of the following (C), low 1 0 less than 1 0 Omega / mouth in the resin composition of the present invention the surface gives the resistivity ⁇ Pi 1 0 1 0 ⁇ ⁇ low volume resistivity of less than cm.
  • thermoplastic E elastomer (B) a lithium salt (C) It is presumed that coordination results in stable and efficient ionic conduction.
  • the thermoplastic elastomer (B) with a polyether block as the soft segment is a styrene resin ( In combination with D), the resin composition of the present invention has a reinforcing effect and achieves a high balance between impact resistance and rigidity. It is possible to cause ionic conduction in combination with a sodium salt (C), and a polymer having such a polyether structure can be exemplified by polyethylene oxide. In this case, a polyether block is used as a soft segment.
  • thermoplastic elastomer (B) Unlike the thermoplastic elastomer (B), it cannot exert the reinforcing effect in combination with the following styrenic resin (D), and the addition of a large amount of highly crystalline polyethylene oxide leads to styrene. Moldability of resin It is also a problem that goodness is lost.
  • thermoplastic elastomer (B) having a polyether block as a soft segment examples include polyester thermoplastic elastomers composed of polyether block polyesters, and polyamide thermoplastic elastomers such as polyether block polyamides and polyether ester amides. 1.Examples include polyurethane-based thermoplastic elastomers such as polyether block urethane and polyetherenoester urethane, and polyolefin-based thermoplastic elastomers composed of polyether block polyolefins. Can be used.
  • Thermoplastic gels and tomas that have generally available polyether blocks as soft segments are structural units and degrees of polymerization of polyether blocks, structural units and degrees of polymerization of hard segments, melting points and solutions of thermoplastic elastomers. Different viscosities are provided. There is no limitation on the elements that characterize these thermoplastic elastomers.However, in order to achieve a high balance between surface resistivity and volume resistivity, surface hardness, and physical properties in the resin composition of the present invention, the main components of the polyether block are: It is preferred that the unit is ethylene oxide and the content of the polyether block in the thermoplastic elastomer is 30 to 85% by weight. More preferably, a polyester-based thermoplastic elastomer and a polyamide-based thermoplastic elastomer which satisfy the above requirements are used.
  • thermoplastic elastomers may be blended to form a thermoplastic elastomer (B).
  • main structural unit of the polyether blocks is that Echireno Kishido, the content of polyether blocks in the thermoplastic elastomer one are 3 0-8 5 weight 0/0, polyester thermoplastic elastomer ⁇ Pi made of Polyamide It preferably contains at least one member selected from the group consisting of thermoplastic elastomers.
  • the -Transparent HIPS is used for the rubber-reinforced styrene resin (A), and the thermoplastic elastomer (B), whose soft segment is a polyether block, has a refractive index with the continuous phase of the transparent HIPS (based on JISK 7105).
  • the difference in refractive index is 0.02 or less, transparency can be imparted to the resin composition of the present invention.
  • the refractive index of the discontinuous phase of the thermoplastic elastomer (B) and the transparent HIPS must be highly matched.
  • the resin composition of the present invention For electronic component transportation materials and the like in which the resin composition of the present invention is usefully used, it is substantially necessary that the presence or absence of the contents can be determined, that is, the total light transmittance is about 60 to 80%.
  • the difference between the refractive indices of not more than 0.02 is within an allowable range (a plurality of thermoplastic elastomers can be blended to form a thermoplastic elastomer (B).
  • the transparent HIPS Transparency can be imparted to the resin composition of the present invention by containing, as a main component, a thermoplastic elastomer having a difference in refractive index from the continuous phase of not more than 0.02.
  • the lithium salt (C) represented by the following formula (1) is a substance that exhibits ionic conduction by ion dissociation.
  • a substance exhibiting ion conduction by ion dissociation inorganic salts and organic salts of alkali metals and alkaline earth metals are generally known.
  • the lithium salt (C) represented by the following (1) is classified as an organic salt of an alkali metal.
  • lithium metal has the smallest ionic radius and the highest degree of freedom of ion transfer, such as lithium cation, Since it is made of anion that has both high thermal stability due to organic structure and high ion dissociation degree due to trifluoro group with strong electron withdrawing power, it excels in obtaining excellent antistatic properties with a small amount of addition. .
  • Z represents a trifluoromethanesulfonyl group
  • n an integer of 1 to 3
  • Tris (trifluoromethanesulfonyl) methanelithium where n 3 and Y is carbon Since methane lithium has a large molecular weight of anion, it is necessary to increase the amount of addition even though the ion dissociation degree is high.
  • Lithium trifluoromethanesulfonate and lithium bis (trifluoromethanesulfonyl) imid are preferred because they can take advantage of the high degree of ionic dissociation and provide excellent antistatic properties with a small amount of addition.
  • a plurality of lithium salts may be blended to form lithium salt (C).
  • lithium trifluoromethanesulfonate, bis (trifluoromethanesulfonate G) It preferably contains at least one kind of imidolithium.
  • the lithium salt (C) can be blended, melted, kneaded, and granulated as it is.
  • the above-mentioned thermoplastic elastomer (B) In order to selectively disperse and enhance the ion conductivity, a compound represented by the following formula (2) at a concentration of 10 to 70% by weight, preferably 20 to 70% by weight, more preferably 30 to 70% by weight is used. It can also be formulated in the form of a solution (Cs) dissolved in the product liquid.
  • X represents hydrogen, an alkyl group having 1 to 4 carbon atoms, an acetate residue, a phthalate residue or an adipic ester residue
  • W represents a hydrogen or a methyl group
  • m represents 1 to 9
  • V represents hydrogen or an alkyl group having 1 to 4 carbon atoms.
  • the concentration is 10% by weight. If the amount is less than the above, the amount of the dissolving solution (C s) increases, that is, an excessive amount of the chemical liquid is added, which reduces the moldability of the resin composition and limits the practical temperature, which is not preferable. . Meanwhile, 70 weight. If it exceeds / 0 , the amount of the dissolving solution (C s) is reduced, and the problem of uneven distribution cannot be solved, which is not preferable.
  • the chemical liquid Needs to have a specific structure represented by the above formula (2).
  • a plurality of chemical liquids can be mixed and used.
  • the styrene resin (D) comprising a copolymer of an aromatic vinyl monomer and an unsaturated carboxylic acid compound is obtained by combining the above rubber-reinforced styrene resin (A) with the above thermoplastic elastomer (B).
  • the rubber-reinforced styrenic resin (A) and the thermoplastic elastomer (B) are integrated, and at the same time, the excellent properties of each are synergized, so that the resin composition of the present invention can be used for a long time and repeatedly. Provides a high balance of surface hardness, impact resistance and rigidity that can withstand use.
  • the styrene resin (D) is in the form of a solution (C s) obtained by dissolving the above-mentioned lithium salt (C) in a chemical liquid, the heat resistance of the chemical liquid decreases, By suppressing the rise, the resin composition of the present invention is provided with excellent moldability due to a sufficiently high heat distortion temperature and appropriate fluidity for practical use.
  • the aromatic vinyl monomer that is one of the constituent units of the styrene resin (D) include styrene, a-methinolestyrene, -methinolestyrene, dibininolebenzen, and chlorostyrene.
  • aromatic vinyl monomers are selected.
  • it is styrene.
  • the amount of the aromatic vinyl monomer is preferably from 80 to 98% by weight, more preferably from 85 to 95% by weight. If it is less than 80% by weight, the production of the styrene resin (D) becomes difficult, which is not preferable. On the other hand, if the content exceeds 98% by weight, it is not preferable because the resin composition has a high surface hardness that can withstand long-term use and repeated use, and a high balance between impact resistance and rigidity cannot be obtained.
  • the other constituent unit is an unsaturated carboxylic acid compound.
  • unsaturated carboxylic acid compound copolymerizable with the aromatic vinyl monomer include acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride.
  • One or more of these unsaturated carboxylic acid compounds are selected.
  • These are lylic acid and methacrylic acid. More preferably, it is methacrylic acid.
  • Unsaturation The amount of the rubonic acid compound is preferably from 2 to 20% by weight, more preferably from 5 to 15% by weight.
  • the content is less than 2% by weight, a high surface height that can withstand long-term and repeated use of the resin composition, and a high balance of impact resistance and rigidity cannot be obtained, which is not preferable.
  • it exceeds 20% by weight the production of the styrenic resin (D) becomes difficult, which is undesirable.
  • an unsaturated compound which can be copolymerized with an aromatic vinyl monomer and an unsaturated carboxylic acid can be used as a constituent unit of the styrene resin (D).
  • unsaturated compounds include methyl methacrylate, ethyl methacrylate, ethyl acrylate, and butyl acrylate.
  • the refractive index of the styrene resin (D) can be made close to the refractive index of the continuous phase of the transparent HIPS.
  • the transparency of the resin composition of the present invention using a transparent HIPS having a difference in refractive index between the thermoplastic elastomer (B) and the continuous phase of the transparent HIPS of 0.02 or less can be enhanced.
  • the degree of polymerization of the styrenic resin (D) is not limited, but from the viewpoint of productivity, the viscosity of the 10% by weight methylethylketone solution at 25 ° C is preferably 4 to 16 cp. And more preferably 6 to 12 cp.
  • styrenic resin (D) a method frequently used in the production of GPPS can be used.
  • a raw material solution comprising a styrene monomer, an unsaturated carboxylic acid compound, a polymerization solvent and a polymerization initiator is supplied to a reactor equipped with a stirrer to perform polymerization.
  • ethyl benzene, toluene, xylene and the like can be used as the polymerization solution.
  • an organic peroxide can be used as the polymerization initiator.
  • the polymerization method a bulk polymerization method and a solution polymerization method which are commonly used in the production method of GPPS are used.
  • Either a batch polymerization method or a continuous polymerization method can be used.
  • the polymerization solution exiting the reactor is led to a recovery device.
  • the recovery device can be a device commonly used in the production of GPPS, such as a flash tank system or an extruder with a multi-stage vent.
  • the operating conditions can be the same as those for manufacturing GPPS.
  • At any stage before or after recovering unreacted monomer and polymerization solvent, commonly used for GPPS Of various additives can be added.
  • the resin composition of the present invention comprises a weight ratio of the rubber-reinforced styrene resin (A), the thermoplastic elastomer (B), the lithium salt (C), and the styrene resin (D). Satisfy the following expressions (a) to (c).
  • Rubber-reinforced styrene resin (A) is less than 70 weight 0/0, i.e., when the thermoplastic elastomer one (B) is more than 30 wt% decreases the elastic modulus of the resin composition, also practical temperature is limited It is not preferable.
  • the content of the rubber-reinforced styrene resin (A) exceeds 90% by weight, that is, if the content of the thermoplastic elastomer (B) is less than 10% by weight, the surface resistivity of the resin composition is 10 10 ⁇ . Or the volume resistivity is less than 10 10 ⁇ ⁇ cm, which is not preferable.
  • the thermoplastic elastomer (B) is 100 parts by weight, and the styrene resin (D) is 5 to 100 parts by weight, preferably 10 to 80 parts by weight. If the styrenic luster (D) is less than 5 parts by weight, the abrasion resistance of the resin composition is reduced, and the impact strength and elastic modulus are undesirably reduced. On the other hand, if the styrene-based resin (D) exceeds 100 parts by weight, the surface resistivity and the volume resistivity of the resin composition are undesirably high.
  • the total of the rubber-reinforced styrene resin (A), the thermoplastic elastomer (B) and the styrene resin (D) is 100 parts by weight, and the lithium salt (C) is 0.2 to 1.2, and the weight is 0.2 to 1.2. Parts, preferably 0.2-1.0 parts by weight.
  • the surface resistivity of the lithium salt (C) is 0.5 resin composition is less than double the amount of unit is less than 1 0 1 0 ⁇ port, or a volume resistivity preferably will be not extend below 10 1 0 ⁇ . Cm Absent.
  • the lithium salt (C) exceeds 1.2 parts by weight, the surface resistivity and the volume resistivity no longer decrease, and the cost and performance of the resin and the composition are undesirably reduced.
  • the method of blending, melting, kneading, and granulating (C) and the styrene-based resin (D) is not particularly limited, and a method commonly used in the production of a resin composition can be used.
  • a rubber reinforced styrene resin (A), a thermoplastic elastomer (B), a lithium salt (C), and a styrene resin (D) blended with a drum tumbler, Henschel mixer, etc. are mixed with a Banbury mixer, single screw extrusion.
  • the resin composition can be obtained by melting and kneading using an extruder, a twin-screw extruder, a kneader ruder or the like, and granulating with a rotary cutter, a fan cutter or the like.
  • the melting and kneading process temperatures are preferably at least 20 ° C. higher than the melting point of the thermoplastic elastomer (B) having a polyether block as a soft segment.
  • thermoplastic elastomer (B) and a lithium salt (C) are blended, melted, kneaded, and granulated to produce an intermediate material.
  • the intermediate material and a rubber-reinforced styrene resin It is also possible to use a method of blending, melting, kneading, and granulating A) and the styrene resin (D). This method may be preferable for selectively dispersing the lithium salt (C) in the thermoplastic elastomer (B), but it is not preferable that the number of production steps is increased.
  • the method of blending, melting, kneading, and granulating the lithium salt (C) in the form of a solution (C s) in which the lithium salt (C) is melted in a chemical liquid is not particularly limited.
  • the rubber-reinforced styrene resin (A), thermoplastic elastomer (B), and styrene resin (D), which are solid materials are compounded using a drum tumbler, Henschel mixer, etc.
  • the feedstock is supplied to a feed hopper such as a kneader ruder, etc.
  • a liquid solution of lithium salt (C s), which is a liquid raw material, is injected into a cylinder such as the twin screw extruder or the kneader ruder using a metering pump to melt
  • the resin composition can be obtained by kneading and granulating with a rotary cutter, a fan cutter or the like.
  • the lithium salt (C) By forming the lithium salt (C) into the form of a solution (C s) that is melted in a chemical liquid, the lithium salt (C) can be selectively dispersed in the thermoplastic elastomer (B). Therefore, as described above, first, thermoplastic elastomer (B) and lithium Salt (C) is blended, melted, kneaded, and granulated to produce an intermediate raw material. Next, the intermediate raw material, rubber-reinforced styrene resin (A) and styrene resin (D) are blended, melted, kneaded, This eliminates the need for a method of granulating and can reasonably produce a resin composition.
  • the resin composition of the present invention comprises a rubber-reinforced styrene-based resin (A), a thermoplastic elastomer (B), a lithium salt (C), or a solution (Cs) of the lithium salt, and a styrene-based resin (C).
  • A rubber-reinforced styrene-based resin
  • B thermoplastic elastomer
  • C lithium salt
  • Cs a solution of the lithium salt
  • Cstyrene-based resin C
  • additives commonly used in HIPS, transparent HIPS, etc. such as antioxidants, lubricants, coloring agents, UV-II absorbers, and light stabilizers, are used. Can be added.
  • the resin composition of the present invention is formed into a resin product by a method generally used in HIPS and transparent HIPS such as injection molding, sheet extrusion molding, vacuum molding, profile extrusion molding, and blow molding.
  • the resin product obtained by molding the resin composition of the present invention has excellent antistatic properties, excellent surface hardness, and excellent strength, so that the contents such as electronic component transportation materials can be electrically and physically. It is suitable for protecting applications, especially for transporting electronic parts that are washed repeatedly and used repeatedly.
  • (A) -1 Rubber-reinforced styrenic resin (A) -1 HT 516 manufactured by PS Japan Ltd. was selected.
  • the melt flow rate measured according to IS ⁇ 1 133 is 2.5 gZl 0 min
  • the Charpy impact strength measured according to ISO 179 is 13 kJ / m
  • the flexural modulus measured according to ISO 178 is The Vicat softening temperature, measured according to 2200 MPa, ISO 306, is 95 ° C.
  • (A) I-2 Rubber-reinforced styrene resin by blending 100 parts by weight of HIPS HT 516 manufactured by PS Japan Co., Ltd. with 685 and 110 parts by weight of GP PS manufactured by PS Japan (A) — 2
  • the melt flow rate of this rubber-reinforced styrenic resin (A) -2 measured according to ISO 133 is 2.5 gZl 0 min
  • the Charpy impact strength measured according to ISO 79 is 7 kJZm 2
  • the flexural modulus measured by the method described above is 2700 MPa
  • the vicat softening temperature measured according to ISO 306 is 99 ° C.
  • (A) -3 Rubber-reinforced styrene resin (A) — 3 was selected as SX800, a transparent HI PS manufactured by PS Japan. Melt flow rate measured according to ISO 1 133 is 1.5 gZl 0 min, Charpy impact strength measured according to IS ⁇ 179 is 6 kJ / m 2 , flexural modulus measured according to ISO 178 is 2400 MP a, The Vicat softening temperature measured according to ISO 306 is 96 ° C, and the refractive index measured according to JISK 7105 is 1.54.
  • ( ⁇ ) 1-1 Thermoplastic elastomer with a polyether block as a soft segment.
  • I-2 Thermoplastic elastomer with soft segment of polyether block (ii) — I selected Restat 300 manufactured by Sanyo Chemical Industry Co., Ltd. It is a polyolefin-based thermoplastic elastomer with polyether block as a soft segment.
  • thermoplastic elastomer ( ⁇ ⁇ ⁇ ) -13 having a polyether block as a soft segment.
  • the refractive index measured according to JI ⁇ 7105 of Pelestat NC 7530 is 1.53, and the refractive index measured according to JISK 7105 of Pelestat NC 6321 is 1.51.
  • (C) 1-1 Florad HQ-115 manufactured by Sumitomo 3LM Ltd. was selected as lithium salt (C) -1. It is bis (trifluoromethanesulfonyl) imidolidium.
  • (C s) 1-2 Sanconol PEG 200-50T manufactured by Sanko Chemical Industry Co., Ltd. was selected as the lithium salt solution (C s) -2. 50 weight of lithium trifluoromethanesulfonate. /. It is a solution that is dissolved in polyethylene glycol with a concentration of 200 and a molecular weight of 200.
  • (C s) — 3 Sanconol 0862-10T manufactured by Sanko Chemical Industry Co., Ltd. was selected as the lithium salt solution (C s) _ 3. This is a solution in which lithium trifluoromethanesulfonate is dissolved in bis (butyldiglycol) adipate at a concentration of 10% by weight.
  • (C s) — 4 Lithium salt solution (C s) Sankonol 0862-20 R manufactured by Sanko Chemical Industry Co., Ltd. was selected as 4.
  • Bis (trifluoromethanesulfonyl) imidium is a solution in which lithium (bis) is dissolved in bis (butyldiglycol) adipate at a concentration of 20% by weight.
  • (D) -1 A styrene-based resin (D) -1 was produced using a polymerization apparatus equipped with a complete mixing reactor and a twin-screw extruder with a two-stage vent. A raw material solution consisting of 93 parts by weight of styrene, 7 parts by weight of methacrylic acid, 25 parts by weight of ethylbenzene, and 0.01 part by weight of 1,1, _bis (t-butylperoxy) 3,3,5-trimethylcyclohexane The mixture was supplied to the reactor and polymerized at a polymerization temperature of 135 ° C. until the solid content of the reaction solution became 70% by weight.
  • the reaction solution discharged from the reactor was continuously introduced into an extruder heated to 220 ° C, and unreacted styrene, methacrylic acid and ethylbenzene were recovered.
  • About 1 g of the obtained styrene resin (D) _1 is dissolved in 30 ml of dimethylformamide, and titrated with 0.1N phenol hydroxide (made of ethanol) using 0.1% phenolphthalein as an indicator.
  • the content of the aromatic vinyl monomer and styrene was 91.4% by weight
  • the content of the unsaturated carboxylic acid compound and methacrylic acid was 8.6% by weight.
  • thermoplastic elastomer (B) polyethylene oxide having a molecular weight of 300,000 manufactured by Meisei Chemical Industry Co., Ltd. was selected as the polymer having a polyether structure.
  • sodium dodecylbenzenesulfonate manufactured by Takemoto Yushi Co., Ltd. was selected as the alkali metal organic salt.
  • Table 1 shows the rubber-reinforced styrene resin (A) selected above, the thermoplastic elastomer (B) selected above, the lithium salt (C) selected above, and the styrene resin (D) manufactured above. The weight was measured as shown in the upper row of Table 2.
  • thermoplastic elastomer (B) and lithium salt (C) are blended in a drum tumbler, melted and kneaded in the same direction twin screw extruder, and fan cut.
  • An intermediate material is produced by granulation, and then the intermediate material, rubber-reinforced styrene-based resin (A) and styrene-based resin (D) are blended in a drum tumbler, melted and kneaded by a bidirectional twin screw extruder.
  • Granulation was performed with a rotary cutter to obtain a resin composition (Examples 1 and 2 and Comparative Example 1).
  • sodium dodecylbenzenesulfonate was used instead of the lithium salt (C) (Comparative Example 5)
  • a resin composition was obtained in the same manner.
  • the melting and kneading process temperatures were set in consideration of the melting point of the thermoplastic elastomer (B). Set the extruder temperature to 230 ° C when using (B) -1 with a melting point of 203 ° C, and set the extruder temperature to 190 ° C when using (B) -2 with a melting point of 135 ° C When (B) -3 having a melting point of 176 ° C was used, the set temperature of the extruder was 210 ° C.
  • the resin compositions (Examples 1 to ⁇ and Comparative Examples 1 to 5) produced above were injection-molded into a 100 mm X 10 Omm X 2.5 mm flat plate test piece, and 4 days / 23 ° CZ50% RH. After performing the pretreatment, the initial surface resistivity and the initial volume resistivity were measured according to JIS K6911. Subsequently, the test piece was subjected to a pretreatment of 50% RH at 23 ° C / 23 ° C for 6 months, and then the surface resistivity and the volume resistivity after 6 months were similarly measured. In addition, the test piece was washed with an ultrasonic cleaner for 15 seconds ⁇ 7 days / 23. After 5 cycles of storage at 50% RH, the surface resistivity after water washing and the volume resistivity after water washing were measured in the same manner.
  • the melt flow rate of the resin composition produced above was measured according to IS01133.
  • the resin composition produced above was injection molded into an ISO type A test piece, and the Charpy impact strength was measured according to ISO 179, the flexural modulus according to ISO 178, and the Vicat softening temperature according to IS 306. did.
  • the results of the above physical property measurements are shown in Tables 1 and 2 below.
  • the rubber-reinforced styrene-based resin (A), the thermoplastic elastomer (B), the lithium salt (C), and the styrene-based resin (D) according to the present invention were blended in the amount according to the present invention, melting a resin composition obtained by kneading and granulation, low surface resistivity of less than 10 1 Q Q / mouth and 1 0 1 () ⁇ ⁇ cm under a low volume resistivity, that excellent by the appropriate fluidity It has a high balance of formability, impact resistance and rigidity, and a sufficiently high heat distortion temperature for practical use.
  • Example 7 a transparent HIPS was used as the rubber-based styrene resin (A), and a thermoplastic elastomer (B) whose refractive index difference from the continuous phase of the transparent HIPS was 0.01 was the main component.
  • the total light transmittance at a thickness of 1 mm is 80%, and substantial transparency is obtained.
  • Comparative Example 1 Comparative Example 1, a thermoplastic elastomer one (B) content is fried small outside the scope of the present invention, 1 0 1 0 Omega Zeta low surface resistivity of less than mouth and 1 0 1 low volume of less than 0 Omega ⁇ cm The resistivity has not been obtained.
  • Comparative Example 3 polyethylene oxide having a molecular weight of 300000 was used in place of the thermoplastic elastomer (B) in the range of the present invention, and the fluidity was so high that extrusion molding was difficult. The balance between strength and elasticity is bad.
  • Comparative Example 5 is used dodecylbenzene scan sulfonic acid Natoriumu instead of the lithium salt of the scope of the present invention (C), 1 0 1 0 low surface resistivity of less than ⁇ port and 1 0 1 less than 0 Omega ⁇ cm Low volume resistivity is not obtained.
  • Comparative Example 6 is out of the range of the present invention because the styrene resin (D) is not contained, and both the impact strength and the elastic modulus are extremely low. Its fluidity is so high that it is difficult to extrude it, and its heat distortion temperature is so low that it cannot withstand cargo hold.
  • the rubber reinforced styrenic resin (A) selected above and the thermoplastic elastomer selected above The stomer (B), the lithium salt (C) selected above, and the styrene resin (D) selected above were weighed as shown in the upper row of Table 3.
  • the mixture is divided into small pieces and mixed with a drum tumbler, immediately melted with a bidirectional twin screw extruder, kneaded, and granulated with a rotary cutter.
  • a resin composition (Example 8 and Comparative Example 8) was obtained.
  • the cylinder temperature of the twin screw extruder was 230 ° C.
  • the resin composition prepared above (Example 8 and Comparative Example 8) was extruded into a sheet having a thickness of 2. Omm, subjected to a pretreatment of Z23 ° C / 50% RH for 4 days, and then subjected to JISK 691 1
  • the surface resistivity and the volume resistivity were measured in accordance with JISK5400, and the pencil drawing strength was measured in accordance with JISK5400.
  • the pencil contact strength was determined as follows: "X" ⁇ The drawn part was sharply cut, " ⁇ " ⁇ The drawn part was cut in places, and " ⁇ " ⁇ The touched part was not cut at all.
  • Example 8 the rubber-reinforced styrene-based resin (A), the thermoplastic elastomer (B), the lithium salt (C), and the styrene-based resin (D) according to the present invention were blended in an amount according to the present invention, melted, kneading, and a granulated resin composition, 10 1 () ⁇ / low have a surface resistivity of less than mouth and 1 ⁇ 10 ⁇ ⁇ cm under a low volume resistivity, total Ku scraped not wear to a pencil hardness HB Has sex.
  • Comparative Example 8 is out of the scope of the present invention because the styrene resin (D) is not contained, and the surface hardness is so poor that even a pencil hardness of 5B can be scraped in places.
  • Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 Rubber-reinforced styrene resin (A) (A)-2 (A)-2 (A)-2 (A)-2 (A)-2 ( ⁇ )-1 (A)-2 parts by weight 88 60 75 75 75 80 60 Thermoplastic elastomer (B) (B)-1 (B)-1 (B)-1 (B) — 1 (B)-l (B) — 1 part by weight 8 32 20 20 20 20 20 16 Lithium salt (C) (O-l (C s) — 4 (C s) — 3 Toss / Hodinom (C s) — 4 (C s) -4 parts by weight 0.4 2.0 2.0 1.0 0.4 2.0 2.0 Styrene resin (D) (D)-l (D)-l (D)-1 (D)- l (D)-1 (D)-l (D)-l Parts by weight 4 8 5 5 5 5 5
  • volume resistivity ⁇ 'cm 3X10 11 4X10 o 8 5X10 9 8X10 8 1X10 10 washed with water volume resistivity ⁇ ' cm 3X10 11 9X10 9 1X10 10 1X10 10 Menore Bok Furorei DOO g / lOmm 3.3 4.8 ⁇ 10 5.0 4.1 11 5.2
  • the resin composition of the present invention is preferably used for applications that play a role of protecting the contents electrically and physically, such as materials for transporting electronic components, especially for materials that are repeatedly washed and used repeatedly.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Composition de résine comprenant une résine de styrène renforcé par latex (A), un élastomère thermoplastique (B) contenant un polyéther bloc sous forme de segment mou, un sel lithium (C) représenté par la formule suivante (1) : [Z]nY-Li+ dans laquelle Z représente trifluorométhanesulfonyle ; n est un entier de 1 à 3 ; Y représente oxygène quand n est 1, azote quand n est 2 ou carbone quand n est 3. Cette composition contient également une résine de styrène (D) comprenant un copolymère de monomère de vinyle aromatique avec un composé d'acide carboxylique insaturé, les constituants (A), (B), (C) et (D) ayant été polymérisés selon une proportion répondant aux équations suivantes (a) à (c). 0,7 ≤ (A) / {(A) + (B)} ≤ 0,9 8 (a) ; 0,05 ≤ (D) / (B) ≤ 1,0 (b) ; 0,002 ≤ (C) / {(A) + (B) + (D)} ≤ 0,012 (c).
PCT/JP2003/013268 2002-10-17 2003-10-16 Composition de resine possedant d'excellentes proprietes antistatiques, de durete de surface et de resistance WO2004035685A1 (fr)

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JP2004544973A JPWO2004035685A1 (ja) 2002-10-17 2003-10-16 制電性と表面硬度と強度に優れた樹脂組成物
KR1020047009318A KR100589069B1 (ko) 2002-10-17 2003-10-16 제전성, 표면 경도 및 강도가 우수한 수지 조성물
AU2003273029A AU2003273029A1 (en) 2002-10-17 2003-10-16 Resin composition excellent in antistatic property, surface hardness, and strength

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JP2006089527A (ja) * 2004-09-21 2006-04-06 Ps Japan Corp 持続制電性樹脂組成物
JP2006152036A (ja) * 2004-11-25 2006-06-15 Techno Polymer Co Ltd 熱可塑性樹脂組成物及び成形品
JP2007063303A (ja) * 2005-08-29 2007-03-15 Techno Polymer Co Ltd 制電性樹脂組成物および成形品

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KR100865594B1 (ko) * 2006-11-08 2008-10-27 광 석 서 전자부품용 대전방지 트레이
CN102134365B (zh) * 2011-04-29 2012-11-21 南通普力马弹性体技术有限公司 永久抗静电的热塑性弹性体材料
JP5918529B2 (ja) * 2011-12-28 2016-05-18 積水化成品工業株式会社 ポリスチレン系樹脂粒子の製造方法、予備発泡粒子の製造方法、及び、ビーズ発泡成形体の製造方法
KR101744967B1 (ko) * 2015-05-06 2017-06-09 그레이스 콘티넨탈 코리아 주식회사 대전방지제 제조방법, 이에 의해 제조된 대전방지제 및 이를 포함하는 수지 조성물
KR200484576Y1 (ko) 2017-01-03 2017-09-27 이영종 칫솔
US10765565B2 (en) 2018-01-25 2020-09-08 The Procter & Gamble Company Method for manufacturing topsheets for absorbent articles
CN112243370A (zh) 2018-06-19 2021-01-19 宝洁公司 具有功能成形的顶片的吸收制品及制造方法
US11819393B2 (en) 2019-06-19 2023-11-21 The Procter & Gamble Company Absorbent article with function-formed topsheet, and method for manufacturing
US12053357B2 (en) 2019-06-19 2024-08-06 The Procter & Gamble Company Absorbent article with function-formed topsheet, and method for manufacturing
CN110591049A (zh) * 2019-09-26 2019-12-20 昆山博益鑫成高分子材料有限公司 一种永久抗静电的本色聚氨酯胶辊

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JP2006152036A (ja) * 2004-11-25 2006-06-15 Techno Polymer Co Ltd 熱可塑性樹脂組成物及び成形品
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JP2007063303A (ja) * 2005-08-29 2007-03-15 Techno Polymer Co Ltd 制電性樹脂組成物および成形品

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AU2003273029A1 (en) 2004-05-04
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