WO2017022637A1 - Antistatic resin composition - Google Patents
Antistatic resin composition Download PDFInfo
- Publication number
- WO2017022637A1 WO2017022637A1 PCT/JP2016/072211 JP2016072211W WO2017022637A1 WO 2017022637 A1 WO2017022637 A1 WO 2017022637A1 JP 2016072211 W JP2016072211 W JP 2016072211W WO 2017022637 A1 WO2017022637 A1 WO 2017022637A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- component
- structural unit
- mol
- unit derived
- structural units
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
Definitions
- the present invention relates to an antistatic resin composition. More specifically, the present invention relates to a polyester resin composition having antistatic properties.
- the material used for the tool and the exterior member is required to have a volume resistance value of 10 9 to 10 10 ⁇ ⁇ cm.
- the packaging material is often transparent (at a haze value of 50% or less) so that at least the presence of the contents can be visually recognized.
- the product is visually inspected, or an identification mark attached to the contents. Transparency that can be confirmed (haze value of 15% or less) is required.
- heat applied during the drying process during the manufacture of precision electronic components heat applied during the drying process during manufacture of articles incorporating precision electronic components; precision electronic equipment (articles incorporating precision electronic components), for example, It must be able to withstand the environmental temperature during transportation, storage, and actual use of in-vehicle equipment such as acoustic equipment and information communication equipment; and heat generated during operation of the equipment. It is required to withstand °C.
- Thermoplastic resins have various properties, so that although they are generally highly electrical insulating materials, their volume resistance value is set to 10-9 so that they can be used in the field of precision electronic components. Many techniques for increasing the power to 10 to the 10th power ⁇ ⁇ cm have been proposed and put into practical use.
- a resin composition of a thermoplastic resin and an ionic surfactant such as an alkyl sulfonate and an alkyl benzene sulfonate, particularly an alkyl (aryl) sulfonate surfactant is proposed.
- an ionic surfactant such as an alkyl sulfonate and an alkyl benzene sulfonate, particularly an alkyl (aryl) sulfonate surfactant.
- Examples of the technique include an antistatic thermoplastic resin (for example, polyether ester amide (Patent Document 3), a backbone polymer made of polyamide, a branch polymer made of a block polymer of a polyalkylene ether and a thermoplastic polyester. Graft polymer (Patent Document 4), specific polyamideimide elastomer (Patent Document 5), and reaction product of specific polyethylene glycol, specific non-hindered diisocyanate, and specific aliphatic chain extender glycol (Patent Document) 6) etc.)) is proposed.
- an antistatic thermoplastic resin for example, polyether ester amide (Patent Document 3), a backbone polymer made of polyamide, a branch polymer made of a block polymer of a polyalkylene ether and a thermoplastic polyester.
- Graft polymer Patent Document 4
- specific polyamideimide elastomer Patent Document 5
- these antistatic thermoplastic resins have the property of accelerating deterioration / lower molecular weight of the polyester resin, and the resin composition of the polyester resin and these antistatic thermoplastic resins is For example, there is a problem that molding defects such as burrs and sink marks are likely to occur in an injection molded product.
- polyether ester for example, poly (alkylene oxide) glycol having a specific molecular weight, glycol having 2 to 8 carbon atoms, polyvalent carboxylic acid having 4 to 20 carbon atoms, etc.
- Patent Document 7 a poly (alkylene oxide) glycol having a specific molecular weight such as an aromatic dicarboxylic acid having 4 to 20 carbon atoms, and a glycol having 4 to 10 carbon atoms.
- Patent Document 8 The resulting polyether ester (Patent Document 8), an aromatic dicarboxylic acid having a specific amount of an aromatic dicarboxylic acid substituted with a specific sulfonate group, a poly (alkylene oxide) glycol having a specific molecular weight, and Polyether ester obtained by polycondensation of glycol having 2 to 10 carbon atoms (Patent Document 9), and charcoal Polyetheresters obtained by polycondensation of poly (alkylene oxide) glycols having a specific molecular weight such as aromatic dicarboxylic acids having 4 to 20 carbon atoms and glycols having 4 to 10 carbon atoms (Patent Document 10) are used. It has been proposed. However, the polyether ester alone is not sufficient in antistatic properties.
- Patent Document 12 it is proposed to use a polyester-based resin as a base resin for a crystallization half time from a molten state of at least 5 minutes. However, if the base resin has such characteristics, it does not have high heat resistance.
- An antistatic resin composition that has excellent antistatic properties, particularly antistatic durability, heat resistance, and transparency, and has no problem of outgassing has not yet been proposed.
- An object of the present invention is to provide an antistatic resin composition which is excellent in antistatic properties, particularly antistatic durability, heat resistance, and transparency, and has no problem of outgassing.
- a further problem of the present invention is that the volume resistivity is 10 9 to 10 10 ⁇ ⁇ cm, and the antistatic property is maintained even when washed with water or wiped, and is heat resistant and transparent. It is an object to provide an antistatic resin composition which is excellent in properties and moldability and has no problem of outgassing.
- the present invention (A) 100 parts by mass of a polyester-based resin having the following characteristics (a1) and (a2); and (B) 7 to 25 parts by mass of a polyetherester resin having a structural unit derived from an aromatic polyvalent carboxylic acid substituted with a sulfonate group; Is an antistatic resin composition.
- A1 The total of structural units derived from polyvalent carboxylic acid is 100 mol%, and includes 90 to 100 mol% of structural units derived from terephthalic acid and 10 to 0 mol% of structural units derived from isophthalic acid.
- (A2) 50 to 90 mol% of structural units derived from 1,4-cyclohexanedimethanol, and 2,2,4,4, -tetramethyl- when the total of structural units derived from polyvalent ol is 100 mol% It contains 50 to 10 mol% of structural units derived from 1,3-cyclobutanediol.
- the component (B) is (B1) one or more selected from the group consisting of terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, and ester-forming derivatives thereof Structural units derived from aromatic dicarboxylic acids; (B2) a structural unit derived from an aromatic polyvalent carboxylic acid substituted with a sulfonate group and / or an ester-forming derivative thereof, represented by the following formula (1); (B3) a structural unit derived from a polyalkylene glycol having a number average molecular weight of 200 to 50,000; (B4) a structural unit derived from a glycol having 2 to 10 carbon atoms; Including Here, assuming that the sum of the content of the structural unit derived from the component (b1) and the content of the structural unit derived from the component (b2) is 100 mol%, 98 to 70
- Ar is a group having an aromatic ring structure in which at least three hydrogen atoms are substituted;
- R1 and R2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms;
- M + represents a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion.
- the (C) ionic surfactant is further contained in an amount of 0.5 to 5 parts by mass with respect to 100 parts by mass of the component (A).
- An antistatic resin composition is further contained in an amount of 0.5 to 5 parts by mass with respect to 100 parts by mass of the component (A).
- a fourth invention is the antistatic resin composition according to any one of the first to third inventions, wherein the volume resistivity is 10 9 to 10 10 ⁇ ⁇ cm.
- the fifth invention is an article comprising the antistatic resin composition according to any one of the first to fourth inventions.
- the sixth invention is a precision electronic device comprising the antistatic resin composition according to any one of the first to fourth inventions.
- the antistatic resin composition of the present invention has excellent antistatic properties, particularly antistatic durability, heat resistance, and transparency, and has no problem of outgassing.
- a preferred antistatic resin composition of the present invention has a volume resistivity of 10 9 to 10 10 ⁇ ⁇ cm, and the antistatic property is maintained even when washed with water or wiped off, and is heat resistant. It has excellent properties, transparency, and moldability, and there is no problem of outgassing.
- Precision electronic parts for example, exterior members of precision electronic devices in which precision electronic parts are incorporated as materials such as transport trays, packaging materials, storage and storage equipment, and exterior members for semiconductor wafers, semiconductor elements, and integrated circuits Can be suitably used.
- the antistatic resin composition of the present invention comprises (A) 100 parts by mass of a polyester resin having the following characteristics (a1) and (a2); and (B) an aromatic polyvalent carboxylic acid substituted with a sulfonate group. 7 to 25 parts by mass of a polyetherester resin having a structural unit derived from an acid.
- A1 The total of structural units derived from polyvalent carboxylic acid is 100 mol%, and includes 90 to 100 mol% of structural units derived from terephthalic acid and 10 to 0 mol% of structural units derived from isophthalic acid.
- (A2) 50 to 90 mol% of structural units derived from 1,4-cyclohexanedimethanol, and 2,2,4,4, -tetramethyl- when the total of structural units derived from polyvalent ol is 100 mol% It contains 50 to 10 mol% of structural units derived from 1,3-cyclobutanediol.
- the component (A) includes (a1) 90 to 100 mol% of structural units derived from terephthalic acid, and 10 to 10 structural units derived from isophthalic acid, where the total of structural units derived from polyvalent carboxylic acid is 100 mol%. (A2) 50 to 90 mol%, preferably 55 to 85 mol, of structural units derived from 1,4-cyclohexanedimethanol, where the total of structural units derived from polyvalent ol is 100 mol%.
- the polyvalent carboxylic acid includes its ester-forming derivative. That is, terephthalic acid includes its ester-forming derivatives. Similarly, isophthalic acid includes its ester-forming derivatives.
- the polyvalent ol includes an ester-forming derivative thereof. That is, 1,4-cyclohexanedimethanol includes its ester-forming derivative.
- 2,2,4,4, -tetramethyl-1,3-cyclobutanediol includes its ester-forming derivatives.
- the component (A) may contain structural units derived from other polyvalent carboxylic acids other than terephthalic acid and isophthalic acid, as long as the object of the present invention is not adversely affected.
- the other polyvalent carboxylic acid include orthophthalic acid, naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenyl-3,3′-dicarboxylic acid, diphenyl-4,4 Aromatic polycarboxylic acids such as' -dicarboxylic acid and anthracene dicarboxylic acid; alicyclic polycarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid Examples include acids; aliphatic polycarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic
- the above component (A) is a polyvalent ol other than 1,4-cyclohexanedimethanol and 2,2,4,4, -tetramethyl-1,3-cyclobutanediol, as long as the object of the present invention is not adversely affected.
- the structural unit derived from may be included.
- Examples of the other polyols include ethylene glycol, diethylene glycol, trimethylene glycol, tetramethylene glycol, neopentyl glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, polypropylene glycol, 1, 2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, decamethylene glycol, 3-methyl-1,5-pentane Aliphatic polyhydric alcohols such as diol, 2-methyl-1,3-propanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, glycerin, and trimethylolpropane; xylylene glycol, 4,4′- Aromatic polyols such as dihydroxybiphenyl
- the antistatic resin composition of the present invention Since the component (A) has a high glass transition temperature (usually 90 ° C. or higher, preferably 100 ° C. or higher, more preferably 110 ° C. or higher), the antistatic resin composition of the present invention has excellent heat resistance. Clearly, since the component (A) is highly transparent, amorphous or low crystalline, and has good miscibility with the component (B), the antistatic resin composition of the present invention is transparent. It will be excellent.
- the glass transition temperature is a Diamond DSC type differential scanning calorimeter manufactured by PerkinElmer Japan Co., Ltd., and the sample is heated to 200 ° C. at a heating rate of 50 ° C./min, and at 200 ° C. for 10 minutes. After the temperature is maintained, the temperature is lowered to 50 ° C. at a rate of temperature decrease of 20 ° C./min, held at 50 ° C. for 10 minutes, and then heated to 200 ° C. at a rate of temperature increase of 20 ° C./min.
- the glass transition temperature appearing in the curve measured in Fig. 2 is the midpoint glass transition temperature calculated by drawing according to FIG. 2 of ASTM D3418.
- the proportion of the structural unit derived from each component in the polyester resin can be determined using 13 C-NMR or 1 H-NMR. An example of 1 H-NMR measurement is shown in FIG.
- the 13 C-NMR spectrum can be measured, for example, by dissolving 20 mg of a sample in 0.6 mL of chloroform-d 1 solvent and using a 125 MHz nuclear magnetic resonance apparatus under the following conditions.
- Chemical shift standard Chloroform-d 1 77 ppm
- Measurement mode Single pulse proton broadband decoupling Pulse width 45 ° (5.00 ⁇ s)
- 64K points Observation range 250ppm (-25 to 225ppm)
- the 1 H-NMR spectrum can be measured, for example, by dissolving 20 mg of a sample in 0.6 mL of chloroform-d 1 solvent and using a 400 MHz nuclear magnetic resonance apparatus under the following conditions.
- the attribution of the peak is “Polymer Analysis Handbook (first edition of September 20, 2008, first edition, edited by Japan Analytical Chemistry Society, Polymer Analysis Research Meeting, Asakura Shoten Co., Ltd.), especially pages 496-503” and “ The NMR database (http://polymer.nims.go.jp/NMR/) of the National Institute for Materials Science, National Institute for Materials Science, is used as a reference, and the peak area ratio of each component in the above component (a) is determined. The percentage can be calculated. Note that 13 C-NMR and 1 H-NMR measurements can also be carried out in an analysis organization such as Mitsui Chemical Analysis Center.
- the component (B) is a polyether ester resin having a structural unit derived from an aromatic polyvalent carboxylic acid substituted with a sulfonate group.
- the component (B) is preferably from the viewpoint of antistatic properties and transparency, (B1) one or more selected from the group consisting of terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, and ester-forming derivatives thereof Structural units derived from aromatic dicarboxylic acids;
- (B2) a structural unit derived from an aromatic polyvalent carboxylic acid substituted with a sulfonate group and / or an ester-forming derivative thereof, represented by the following formula (1);
- (B3) a structural unit derived from a polyalkylene glycol having a number average molecular weight of 200 to 50,000;
- (B4) a structural unit derived from a glycol having 2
- the content of the derived structural unit is 10 to 60% by mass; a polyetherester resin.
- Ar is a group having an aromatic ring structure in which at least three hydrogen atoms are substituted;
- R1 and R2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl having 6 to 12 carbon atoms Group;
- M + represents a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion.
- the component (B) is composed of (b1) terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, and ester-forming derivatives thereof. It is preferable that it contains a structural unit derived from one or more aromatic dicarboxylic acids selected from the above because the heat resistance is further improved.
- the component (B) contains a structural unit derived from (b2) an aromatic polyvalent carboxylic acid substituted with a sulfonate group and / or an ester-forming derivative thereof represented by the following formula (1). It is preferable because the antistatic property is further improved.
- Ar in the above formula (1) is a group having an aromatic ring structure in which at least three hydrogen atoms are substituted.
- Examples of Ar in the above formula (1) include a group having a benzene ring structure in which at least three hydrogen atoms are substituted, and a group having a naphthalene ring structure in which at least three hydrogen atoms are substituted. These not only replace three hydrogen atoms with three substituents specified by the above formula (1), but also one or more hydrogen atoms such as an alkyl group, a phenyl group, a halogen group, and an alkoxy group. It may be substituted with a substituent. The substitution position is not limited and can be arbitrarily selected.
- Ar in the formula (1) is preferably a group having a benzene ring structure in which three hydrogen atoms are substituted from the viewpoints of polymerizability, mechanical properties, and color tone.
- R1 in the above formula (1) is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Preferred are alkyl groups having 1 to 3 carbon atoms such as a hydrogen atom, a methyl group, an ethyl group, and a propyl group. In these, as R1 in the said Formula (1), a methyl group and an ethyl group are preferable from a viewpoint of polymerizability, mechanical characteristics, and color tone.
- R2 in the above formula (1) is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
- alkyl groups having 1 to 3 carbon atoms such as a hydrogen atom, a methyl group, an ethyl group, and a propyl group.
- R2 in the above formula (1) a methyl group and an ethyl group are preferable from the viewpoints of polymerizability, mechanical properties, and color tone.
- R1 and R2 may have the same structure or different structures.
- R1 and R2 in the formula (1) can independently take an arbitrary structure within the above range.
- M + in the above formula (1) is a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion.
- M ⁇ +> in the said Formula (1) is multivalent, the number of sulfonic acid groups (part other than M ⁇ +> in the said Formula (1)) corresponding to this correspond.
- M + in the above formula (1) is a divalent metal ion, two sulfonic acid groups (parts other than M + in the above formula (1)) per one metal ion ) Corresponds.
- Examples of the metal ions include alkali metal ions such as sodium ion, potassium ion, and lithium ion; alkaline earth metal ions such as calcium ion and magnesium ion; and zinc ion.
- alkali metal ions such as sodium ion, potassium ion, and lithium ion
- alkaline earth metal ions such as calcium ion and magnesium ion
- zinc ion examples of the tetraalkylphosphonium ion.
- Examples of the tetraalkylphosphonium ion include tetrabutylphosphonium ion and tetramethylphosphonium ion.
- Examples of the tetraalkylammonium ion include tetrabutylammonium ion and tetramethylammonium ion.
- alkali metal ions, tetrabutylammonium ions, and tetrabutylphosphonium ions are preferable from the viewpoints of polymerizability, mechanical properties, antistatic properties, and color tone. More preferred are alkali metal ions and tetrabutylphosphonium ions.
- Examples of the component (b2) that is, the aromatic polyvalent carboxylic acid substituted with a sulfonate group and / or its ester-forming derivative represented by the above formula (1) include 4-sodium sulfo-isophthalic acid.
- the component (b2) includes 4-sodium sulfo-isophthalate dimethyl, 5-sodium sulfo-isophthalate dimethyl, 4-potassium sulfo-isophthalate dimethyl from the viewpoints of polymerizability, mechanical properties, and color tone.
- 4-sodium sulfo-dimethyl isophthalate, 2-sodium sulfo-dimethyl terephthalate, and 2-potassium sulfo-dimethyl terephthalate are preferred.
- the component (B) is derived from the component (b1), where the sum of the content of the structural unit derived from the component (b1) and the content of the structural unit derived from the component (b2) is 100 mol%.
- a structural unit derived from the above component (b2) in an amount of 98 to 70 mol%, preferably 97 to 71 mol%, more preferably 95 to 73 mol%, still more preferably 91 to 75 mol%. It is preferable that the unit is contained in an amount of 2 to 30 mol%, preferably 3 to 29 mol%, more preferably 5 to 27 mol%, still more preferably 9 to 25 mol%.
- the antistatic resin composition of the present invention is The antistatic property is further improved. Moreover, even if washed with water or wiped off, good antistatic properties can be maintained. In addition, it has sufficient molecular weight and crystallinity, and is easy to handle.
- the component (B) contains (b3) a structural unit derived from a polyalkylene glycol having a number average molecular weight of 200 to 50,000, since the antistatic property is further improved.
- Examples of the component (b3) that is, a polyalkylene glycol having a number average molecular weight of 200 to 50,000 include propylene glycol using polyethylene glycol, polypropylene glycol, and ethylene glycol as main monomers (usually 60 mol% or more, preferably 80 mol% or more).
- a small amount (usually 10 mol% or less, preferably 5 mol% or less, more preferably 1 mol% or less) of a polyaromatic copolymer having ethylene as a comonomer and alkylene glycol such as ethylene glycol or propylene glycol as a main monomer.
- Examples thereof include a copolymer having a valence ol as a comonomer, and a mixture thereof.
- the number average molecular weight of the component (b3) is 200 to 50000, preferably 500 to 30000, more preferably 1000 to 20000 from the viewpoints of antistatic properties, dispersibility, and heat resistance.
- the content of the structural unit derived from the component (b3) in the component (B) is from 10 to 60% by mass, preferably from 15 to 55% by mass, from the viewpoint of antistatic properties, handleability, and heat resistance.
- the amount is preferably 20 to 50% by mass.
- the content of the structural unit derived from the component (b1), the content of the structural unit derived from the component (b2), the content of the structural unit derived from the component (b3), and the component (b4) The sum of the content of structural units derived from is 100% by mass.
- the component (B) contains (b4) a structural unit derived from a glycol having 2 to 10 carbon atoms because the antistatic property, handleability and heat resistance are further improved.
- Examples of the component (b4) that is, a glycol having 2 to 10 carbon atoms, include ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,6-hexanediol.
- Aliphatic glycols such as 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 1,2-cyclohexanediol, and 1,4-cyclohexanediol; having an ether bond such as diethylene glycol
- glycols having a thioether bond such as thiodiethanol.
- 1,6-hexanediol, ethylene glycol, and diethylene glycol are preferable from the viewpoint of antistatic properties, crystallinity, and handleability.
- ethylene glycol, and diethylene glycol are preferable from the viewpoint of antistatic properties, crystallinity, and handleability.
- One or more of these can be used as the component (b4).
- a DIN Ubbelohde viscometer capillary diameter 0.63 mm
- a mixed solvent of phenol / tetrachloroethane mass ratio 60/40
- the reduced viscosity measured under conditions of a concentration of 1.2 g / dl and a temperature of 35 ° C. is preferably 0.2 cm 3 / g or more, more preferably 0.25 cm, from the viewpoint of antistatic properties, heat resistance, and mechanical properties.
- the method for obtaining the component (B) using the components (b1) to (b4) is not particularly limited, and can be performed by any method.
- the component (B) can be obtained by heat-melting the components (b1) to (b4) at 150 to 300 ° C. in the presence of a transesterification catalyst to cause a polycondensation reaction.
- the transesterification catalyst is not particularly limited, and any transesterification catalyst can be used.
- the transesterification catalyst include antimony compounds such as antimony trioxide; tin compounds such as stannous acetate, dibutyltin oxide, and dibutyltin diacetate; titanium compounds such as tetrabutyl titanate; zinc compounds such as zinc acetate.
- a calcium compound such as calcium acetate; and alkali metal salts such as sodium carbonate and potassium carbonate. Of these, tetrabutyl titanate is preferred. One or more of these can be used as the transesterification catalyst.
- the amount of the transesterification catalyst used is not particularly limited, but is usually 0.01 to 0.5 mol%, preferably 0.03 to 0.3 mol%, relative to 1 mol of the component (b1).
- the polycondensation reaction is carried out at 150 to 250 ° C., preferably 150 to 200 ° C. for about 1 to 20 hours while distilling off the distillate, and then the temperature is 180 to 300 ° C., preferably 200 to 280 ° C.
- the temperature is preferably raised to 220 to 260 ° C. and further for about 1 to 20 hours.
- the component (B) can have a reduced viscosity within a preferred range.
- the blending amount of the component (B) is 7 parts by mass or more, preferably 9 parts by mass or more, more preferably 12 parts by mass or more, from the viewpoint of antistatic properties with respect to 100 parts by mass of the component (A). .
- it is 25 parts by mass or less, preferably 22 parts by mass or less, more preferably 20 parts by mass or less.
- Ionic surfactant (optional component):
- the antistatic resin composition of the present invention expresses sufficient antistaticity without using an ionic surfactant, but it is necessary to use an ionic surfactant. It is not excluded.
- the antistatic resin composition of the present invention is used when the antistatic resin composition is used for, for example, an application in which the initial antistatic property is particularly important, or an application in which the necessity of considering outgas and bleedout problems is low.
- the composition may comprise an ionic surfactant.
- the amount of the component (C) ionic surfactant used is not particularly limited because it is an optional component, but may be 0.5 to 5 parts by mass with respect to 100 parts by mass of the component (A). .
- component (C) examples include an organic sulfonic acid type surfactant composed of an organic sulfonic acid and a base.
- organic sulfonic acid examples include alkyl benzene sulfonic acids having 6 to 18 carbon atoms in the alkyl group such as octyl benzene sulfonic acid, dodecyl benzene sulfonic acid, dibutyl benzene sulfonic acid, and dinonyl benzene sulfonic acid; and dimethylnaphthalene And alkylnaphthalenesulfonic acid having 2 to 18 carbon atoms in the alkyl group such as sulfonic acid, diisopropylnaphthalenesulfonic acid, and dibutylnaphthalenesulfonic acid. Among these, dodecylbenzenesulfonic acid and dimethylnaphthalenesulfonic acid are preferable. One or more of these organic sulfonic acids can be used.
- Examples of the base include alkali metals such as lithium, sodium, and potassium; phosphonium compounds such as tetrabutylphosphonium, tributylbenzylphosphonium, triethylhexadecylphosphonium, and tetraphenylphosphonium; and tetrabutylammonium, tributylbenzylammonium, And ammonium compounds such as triphenylbenzylammonium.
- alkali metals such as lithium, sodium, and potassium
- phosphonium compounds such as tetrabutylphosphonium, tributylbenzylphosphonium, triethylhexadecylphosphonium, and tetraphenylphosphonium
- tetrabutylammonium tributylbenzylammonium
- ammonium compounds such as triphenylbenzylammonium.
- sodium, potassium, tetramethylphosphonium, tetraethylphosphonium, tetrahexylphosphonium, tetraoctylphosphonium, tetrabutylphosphonium, tributylbenzylphosphonium, triethylhexadecylphosphonium, and tetraphenylphosphonium are preferred.
- One or more of these can be used as the base.
- Preferred examples of the component (C) include those in which the base is a phosphonium compound, for example, tetrabutylphosphonium dodecylbenzenesulfonate, from the viewpoint of suppressing outgas and antistatic properties.
- the base is a phosphonium compound, for example, tetrabutylphosphonium dodecylbenzenesulfonate, from the viewpoint of suppressing outgas and antistatic properties.
- the volume resistivity of the antistatic resin composition of the present invention is preferably 10 10 ⁇ ⁇ cm or less, more preferably 10 9 to 10 10 ⁇ ⁇ cm. More preferably, the volume resistivity is 10 9 to 10 10 ⁇ ⁇ cm, and the antistatic property is maintained even after washing with water or wiping.
- the volume resistivity is a value measured according to the following test (2).
- the outgas amount of the antistatic resin composition of the present invention is preferably 2 ⁇ g / g or less, more preferably 1 ⁇ g / g or less. If it is a normal use, it can be preferably used when the outgas amount is 2 ⁇ g / g or less. Even applications that require a particularly low outgas amount, such as precision electronic equipment, can be preferably used when the outgas amount is 1 ⁇ g / g or less. In this specification, the amount of outgas is the amount ( ⁇ g) of outgas generated from 1 g of the sample, measured according to the following test (5).
- the antistatic resin composition of the present invention may further include a thermoplastic resin other than the component (A) and the component (B), and an interface other than the component (C).
- Activators, heat stabilizers, antioxidants, hydrolysis inhibitors, metal deactivators, UV absorbers, antistatic agents, lubricants, colorants, and the like can be included.
- the antistatic resin composition of the present invention contains a heat stabilizer or an antioxidant. Even when molding a large molded product, molding troubles such as coloring and burning can be prevented. It is preferable to include a metal deactivator in the antistatic resin composition of the present invention. Even when used in parts that come into contact with metal, corrosion and discoloration of the contact portion can be prevented.
- antioxidants examples include 2,6-di-tert-p-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4,4 Phenolic antioxidants such as 2-dihydroxydiphenyl and tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane; phosphite antioxidants; and thioether antioxidants it can. Of these, phenolic antioxidants and phosphite antioxidants are preferred.
- the antistatic resin composition of the present invention can be produced by melt-kneading the component (A), the component (B), and an optional component in an arbitrary order or simultaneously.
- the method of melt kneading is not particularly limited, and a known method can be used.
- a single screw extruder, a twin screw extruder, a roll, a mixer, or various kneaders can be used.
- a mixer or kneader for example, it is preferable to perform melt-kneading under conditions of a discharge temperature of 240 to 260 ° C.
- melt kneading at a screw rotation speed of 50 to 500 rpm and a kneading temperature of 240 to 260 ° C., for example.
- the antistatic resin composition of the present invention can be molded into an arbitrary molded product using a known molding method.
- the molding method include a general injection molding method, insert molding method, two-color molding method, sandwich molding method, gas injection method, profile extrusion molding method, two-color extrusion molding method, coating molding method, and sheet
- a film extrusion method can be used.
- Measuring method (1) Formability: Using an injection molding machine with a clamping force of 120 tons, an injection molded plate with a length of 64.4 mm, a width of 64.4 mm, and a thickness of 3 mm is obtained under the conditions of a cylinder temperature of 240 to 260 ° C., a mold temperature of 50 ° C., and a cooling time of 5 minutes. Molded. The obtained plate was visually observed and evaluated according to the following criteria. ⁇ : Sink and warp are not recognized. X: Sink or warp, or sink and warp
- Outgas amount For the measurement, a heat desorption gas chromatograph mass spectrometer manufactured by PerkinElmer was used.
- Collection of outgas by thermal desorption method The resin composition is frozen and pulverized to obtain a pulverized product of 2 mm square or less, and 0.1 g of the pulverized product obtained above is placed in a sample holder of the collection unit of the above apparatus and heated at 120 ° C. for 10 minutes to generate generated volatilization. The substance was collected in a cold trap tube maintained at 5 ° C. using helium gas as the carrier gas.
- Thermal deformation temperature (heat resistance): In accordance with ASTM D648-07, using an injection molding machine with a clamping force of 120 ton, a cylinder temperature of 240 to 260 ° C, a mold temperature of 50 ° C, a cooling time of 5 minutes, a length of 127mm, a height of 13mm, A test piece having a thickness of 6 mm was used, and measurement was performed under the conditions of a fulcrum distance of 100.0 mm (Method B), a load of 1.82 MPa, and a temperature increase rate of 2 ° C.
- Polyester resin (A-1) The sum of structural units derived from polyvalent carboxylic acid is defined as 100 mol%, the structural unit derived from terephthalic acid is defined as 100 mol%, and the sum of structural units derived from polyvalent ol is defined as 100 mol%.
- (A-2) The sum of the structural units derived from polyvalent carboxylic acid is defined as 100 mol%, the structural unit derived from terephthalic acid is defined as 100 mol%, and the sum of structural units derived from polyvalent ol is defined as 100 mol%.
- (B) Polyetherester resin (B-1) A polyetherester resin obtained in accordance with the description in paragraph 0063 and Reference Example 1 of JP-A-8-283548.
- the component (b1) is dimethyl terephthalate
- the component (b2) is dimethyl 5-sodium sulfoisophthalate
- the component (b3) is polyethylene glycol (number average molecular weight 20000)
- the component (b4) is 1,4-butanediol. .
- the structural unit derived from the component (b1) is 75 mol%, 25 mol% of structural units derived from the component (b2).
- the content of the structural unit derived from the component (b3) is 11% by mass, where the sum of the content of the structural unit is 100% by mass.
- the component (b1) is dimethyl terephthalate
- the component (b2) is dimethyl 5-sodium sulfoisophthalate
- the component (b3) is polyethylene glycol (number average molecular weight 20000)
- the component (b4) is 1,4-butanediol.
- the structural unit derived from the component (b1) is 85 mol%, 15 mol% of structural units derived from the component (b2).
- the content of the structural unit derived from the component (b3) is 20% by mass, where the sum of the content of the structural unit is 100% by mass.
- (B-3) A polyetherester resin obtained according to the description in paragraph 0065 and Reference Example 3 of JP-A-8-283548.
- the component (b1) is dimethyl terephthalate
- the component (b2) is dimethyl 5-sodium sulfoisophthalate
- the component (b3) is polyethylene glycol (number average molecular weight 20000)
- the component (b4) is 1,4-butanediol. .
- the structural unit derived from the component (b1) is 75 mol%, 25 mol% of structural units derived from the component (b2).
- Content of structural unit derived from component (b1), content of structural unit derived from component (b2), content of structural unit derived from component (b3), and derived from component (b4) The content of the structural unit derived from the component (b3) is 20% by mass, where the sum of the content of the structural unit is 100% by mass.
- the component (b1) is dimethyl terephthalate
- the component (b2) is dimethyl 5-sodium sulfoisophthalate
- the component (b3) is polyethylene glycol (number average molecular weight 4000)
- the component (b4) is 1,4-butanediol.
- the structural unit derived from the component (b1) is 75 mol%, 25 mol% of structural units derived from the component (b2).
- the content of the structural unit derived from the component (b3) is 20% by mass, where the sum of the content of the structural unit is 100% by mass.
- C Ionic surfactant (C-1) Sodium dodecylbenzenesulfonate from Kanto Chemical Co., Inc.
- Examples 1-11, Examples 1C-7C Using a 20 mm ⁇ same-direction biaxial kneader, a blend having a blending ratio shown in any one of Tables 1 to 3 was melt-kneaded at a preset temperature of 240 to 260 ° C. to obtain a resin composition. The above tests (1) to (7) were conducted. The results are shown in any one of Tables 1 to 3.
- the resin composition of the present invention is excellent in moldability, antistatic properties, antistatic durability, low outgas properties, transparency, and heat resistance.
Landscapes
- 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)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
(A)下記特性(a1)、及び(a2)を有するポリエステル系樹脂 100質量部;及び、
(B)スルホン酸塩基で置換された芳香族多価カルボン酸に由来する構造単位を有するポリエーテルエステル樹脂 7~25質量部;
を含む制電性樹脂組成物である。
(a1)多価カルボン酸に由来する構造単位の総和を100モル%として、テレフタル酸に由来する構造単位90~100モル%、及びイソフタル酸に由来する構造単位10~0モル%を含む。
(a2)多価オールに由来する構造単位の総和を100モル%として、1,4-シクロヘキサンジメタノールに由来する構造単位50~90モル%、及び2,2,4,4,-テトラメチル-1,3-シクロブタンジオールに由来する構造単位50~10モル%を含む。 That is, the present invention
(A) 100 parts by mass of a polyester-based resin having the following characteristics (a1) and (a2); and
(B) 7 to 25 parts by mass of a polyetherester resin having a structural unit derived from an aromatic polyvalent carboxylic acid substituted with a sulfonate group;
Is an antistatic resin composition.
(A1) The total of structural units derived from polyvalent carboxylic acid is 100 mol%, and includes 90 to 100 mol% of structural units derived from terephthalic acid and 10 to 0 mol% of structural units derived from isophthalic acid.
(A2) 50 to 90 mol% of structural units derived from 1,4-cyclohexanedimethanol, and 2,2,4,4, -tetramethyl- when the total of structural units derived from polyvalent ol is 100 mol% It contains 50 to 10 mol% of structural units derived from 1,3-cyclobutanediol.
(b1)テレフタル酸、2,6-ナフタレンジカルボン酸、2,7-ナフタレンジカルボン酸、ビフェニル-4,4’-ジカルボン酸、及びこれらのエステル形成性誘導体からなる群から選択される1種以上の芳香族ジカルボン酸に由来する構造単位;
(b2)下記式(1)で表される、スルホン酸塩基で置換された芳香族多価カルボン酸及び/又はそのエステル形成性誘導体に由来する構造単位;
(b3)数平均分子量200~50000のポリアルキレングリコールに由来する構造単位;及び、
(b4)炭素数2~10のグリコールに由来する構造単位;
を含み、
ここで上記成分(b1)に由来する構造単位の含有量と上記成分(b2)に由来する構造単位の含有量との和を100モル%として、
上記成分(b1)に由来する構造単位を98~70モル%、
上記成分(b2)に由来する構造単位を2~30モル%となる量で含み;
上記成分(b1)に由来する構造単位の含有量、上記成分(b2)に由来する構造単位の含有量、 上記成分(b3)に由来する構造単位の含有量、及び上記成分(b4)に由来する構造単位の含有量の和を100質量%として、
上記成分(b3)に由来する構造単位の含有量が10~60質量%である;
ポリエーテルエステル樹脂である
第1の発明に記載の制電性樹脂組成物である。
Arは少なくとも3つの水素原子が置換された芳香環構造を有する基;
R1及びR2はそれぞれ独立に水素原子、炭素数1~6のアルキル基又は炭素数6~12のアリール基;
M+は金属イオン、テトラアルキルホスホニウムイオン又はテトラアルキルアンモニウムイオンを表す。 In a second invention, the component (B) is
(B1) one or more selected from the group consisting of terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, and ester-forming derivatives thereof Structural units derived from aromatic dicarboxylic acids;
(B2) a structural unit derived from an aromatic polyvalent carboxylic acid substituted with a sulfonate group and / or an ester-forming derivative thereof, represented by the following formula (1);
(B3) a structural unit derived from a polyalkylene glycol having a number average molecular weight of 200 to 50,000;
(B4) a structural unit derived from a glycol having 2 to 10 carbon atoms;
Including
Here, assuming that the sum of the content of the structural unit derived from the component (b1) and the content of the structural unit derived from the component (b2) is 100 mol%,
98 to 70 mol% of structural units derived from the component (b1),
Containing structural units derived from the component (b2) in an amount of 2 to 30 mol%;
Content of structural unit derived from component (b1), content of structural unit derived from component (b2), content of structural unit derived from component (b3), and derived from component (b4) The sum of the content of structural units to be 100% by mass
The content of structural units derived from the component (b3) is 10 to 60% by mass;
The antistatic resin composition according to the first invention, which is a polyetherester resin.
Ar is a group having an aromatic ring structure in which at least three hydrogen atoms are substituted;
R1 and R2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms;
M + represents a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion.
(a1)多価カルボン酸に由来する構造単位の総和を100モル%として、テレフタル酸に由来する構造単位90~100モル%、及びイソフタル酸に由来する構造単位10~0モル%を含む。
(a2)多価オールに由来する構造単位の総和を100モル%として、1,4-シクロヘキサンジメタノールに由来する構造単位50~90モル%、及び2,2,4,4,-テトラメチル-1,3-シクロブタンジオールに由来する構造単位50~10モル%を含む。 The antistatic resin composition of the present invention comprises (A) 100 parts by mass of a polyester resin having the following characteristics (a1) and (a2); and (B) an aromatic polyvalent carboxylic acid substituted with a sulfonate group. 7 to 25 parts by mass of a polyetherester resin having a structural unit derived from an acid.
(A1) The total of structural units derived from polyvalent carboxylic acid is 100 mol%, and includes 90 to 100 mol% of structural units derived from terephthalic acid and 10 to 0 mol% of structural units derived from isophthalic acid.
(A2) 50 to 90 mol% of structural units derived from 1,4-cyclohexanedimethanol, and 2,2,4,4, -tetramethyl- when the total of structural units derived from polyvalent ol is 100 mol% It contains 50 to 10 mol% of structural units derived from 1,3-cyclobutanediol.
上記成分(A)は、(a1)多価カルボン酸に由来する構造単位の総和を100モル%として、テレフタル酸に由来する構造単位90~100モル%、及びイソフタル酸に由来する構造単位10~0モル%;を含み、(a2)多価オールに由来する構造単位の総和を100モル%として、1,4-シクロヘキサンジメタノールに由来する構造単位50~90モル%、好ましくは55~85モル%、より好ましくは60~80モル%、及び2,2,4,4,-テトラメチル-1,3-シクロブタンジオールに由来する構造単位50~10モル%、好ましくは45~15モル%、より好ましくは40~20モル%;を含むポリエステル系樹脂である。ここで多価カルボン酸は、そのエステル形成性誘導体を含む。即ち、テレフタル酸は、そのエステル形成性誘導体を含む。同様にイソフタル酸は、そのエステル形成性誘導体を含む。ここで多価オールは、そのエステル形成性誘導体を含む。即ち、1,4-シクロヘキサンジメタノールは、そのエステル形成性誘導体を含む。同様に2,2,4,4,-テトラメチル-1,3-シクロブタンジオールは、そのエステル形成性誘導体を含む。 (A) Polyester resin:
The component (A) includes (a1) 90 to 100 mol% of structural units derived from terephthalic acid, and 10 to 10 structural units derived from isophthalic acid, where the total of structural units derived from polyvalent carboxylic acid is 100 mol%. (A2) 50 to 90 mol%, preferably 55 to 85 mol, of structural units derived from 1,4-cyclohexanedimethanol, where the total of structural units derived from polyvalent ol is 100 mol%. %, More preferably 60 to 80 mol%, and 50 to 10 mol%, preferably 45 to 15 mol% of structural units derived from 2,2,4,4, -tetramethyl-1,3-cyclobutanediol, and more A polyester-based resin containing 40 to 20 mol% is preferable. Here, the polyvalent carboxylic acid includes its ester-forming derivative. That is, terephthalic acid includes its ester-forming derivatives. Similarly, isophthalic acid includes its ester-forming derivatives. Here, the polyvalent ol includes an ester-forming derivative thereof. That is, 1,4-cyclohexanedimethanol includes its ester-forming derivative. Similarly, 2,2,4,4, -tetramethyl-1,3-cyclobutanediol includes its ester-forming derivatives.
ケミカルシフト基準 クロロホルム-d1:77ppm
測定モード シングルパルスプロトンブロードバンドデカップリング
パルス幅 45°(5.00μ秒)
ポイント数 64K
観測範囲 250ppm(-25~225ppm)
繰り返し時間 5.5秒
積算回数 256回
測定温度 23℃
ウインドウ関数 exponential(BF:1.0Hz) The 13 C-NMR spectrum can be measured, for example, by dissolving 20 mg of a sample in 0.6 mL of chloroform-d 1 solvent and using a 125 MHz nuclear magnetic resonance apparatus under the following conditions.
Chemical shift standard Chloroform-d 1 : 77 ppm
Measurement mode Single pulse proton broadband decoupling Pulse width 45 ° (5.00 μs)
64K points
Observation range 250ppm (-25 to 225ppm)
Repeat time 5.5 seconds Accumulation 256 times Measurement temperature 23 ° C
Window function exponential (BF: 1.0Hz)
ケミカルシフト基準 クロロホルム:7.24ppm
測定モード シングルパルス
パルス幅 45°(5.14μ秒)
ポイント数 16k
測定範囲 15ppm(-2.5~12.5ppm)
繰り返し時間 7.8秒
積算回数 64回
測定温度 23℃
ウインドウ関数 exponential(BF:0.18Hz) The 1 H-NMR spectrum can be measured, for example, by dissolving 20 mg of a sample in 0.6 mL of chloroform-d 1 solvent and using a 400 MHz nuclear magnetic resonance apparatus under the following conditions.
Chemical Shift Standard Chloroform: 7.24ppm
Measurement mode Single pulse Pulse width 45 ° (5.14 μs)
Number of points 16k
Measurement range 15ppm (-2.5 to 12.5ppm)
Repetition time 7.8 seconds Integration count 64 times Measurement temperature 23 ° C
Window function exponential (BF: 0.18Hz)
上記成分(B)は、スルホン酸塩基で置換された芳香族多価カルボン酸に由来する構造単位を有するポリエーテルエステル樹脂である。上記成分(B)は、制電性、及び透明性の観点から、好ましくは、
(b1)テレフタル酸、2,6-ナフタレンジカルボン酸、2,7-ナフタレンジカルボン酸、ビフェニル-4,4’-ジカルボン酸、及びこれらのエステル形成性誘導体からなる群から選択される1種以上の芳香族ジカルボン酸に由来する構造単位;
(b2)下記式(1)で表される、スルホン酸塩基で置換された芳香族多価カルボン酸及び/又はそのエステル形成性誘導体に由来する構造単位;
(b3)数平均分子量200~50000のポリアルキレングリコールに由来する構造単位;及び、
(b4)炭素数2~10のグリコールに由来する構造単位;
を含み、ここで上記成分(b1)に由来する構造単位の含有量と上記成分(b2)に由来する構造単位の含有量との和を100モル%として、上記成分(b1)に由来する構造単位を98~70モル%、上記成分(b2)に由来する構造単位を2~30モル%となる量で含み;上記成分(b1)に由来する構造単位の含有量、上記成分(b2)に由来する構造単位の含有量、上記成分(b3)に由来する構造単位の含有量、及び上記成分(b4)に由来する構造単位の含有量の和を100質量%として、上記成分(b3)に由来する構造単位の含有量が10~60質量%である;ポリエーテルエステル樹脂である。 (B) Polyetherester resin:
The component (B) is a polyether ester resin having a structural unit derived from an aromatic polyvalent carboxylic acid substituted with a sulfonate group. The component (B) is preferably from the viewpoint of antistatic properties and transparency,
(B1) one or more selected from the group consisting of terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, and ester-forming derivatives thereof Structural units derived from aromatic dicarboxylic acids;
(B2) a structural unit derived from an aromatic polyvalent carboxylic acid substituted with a sulfonate group and / or an ester-forming derivative thereof, represented by the following formula (1);
(B3) a structural unit derived from a polyalkylene glycol having a number average molecular weight of 200 to 50,000;
(B4) a structural unit derived from a glycol having 2 to 10 carbon atoms;
Wherein the sum of the content of the structural unit derived from the component (b1) and the content of the structural unit derived from the component (b2) is 100 mol%, and the structure derived from the component (b1). Containing 98 to 70 mol% of units and 2 to 30 mol% of structural units derived from the component (b2); content of structural units derived from the component (b1); The sum of the content of the structural unit derived from the content of the structural unit derived from the component (b3) and the content of the structural unit derived from the component (b4) is 100% by mass. The content of the derived structural unit is 10 to 60% by mass; a polyetherester resin.
本発明の制電性樹脂組成物は、上述したように、イオン性界面活性剤を使用しなくても十分な制電性を発現するものであるが、イオン性界面活性剤を使用することを排除するものではない。制電性樹脂組成物を、例えば、初期の制電性が特に重視される用途や、アウトガスやブリードアウトの問題を考慮する必要性が低い用途に用いる場合には、本発明の制電性樹脂組成物はイオン性界面活性剤を含むものであってよい。 (C) Ionic surfactant (optional component):
As described above, the antistatic resin composition of the present invention expresses sufficient antistaticity without using an ionic surfactant, but it is necessary to use an ionic surfactant. It is not excluded. The antistatic resin composition of the present invention is used when the antistatic resin composition is used for, for example, an application in which the initial antistatic property is particularly important, or an application in which the necessity of considering outgas and bleedout problems is low. The composition may comprise an ionic surfactant.
(1)成形性:
型締め力120tonの射出成形機を使用し、縦64.4mmm、横64.4mm、厚み3mmの射出成形プレートを、シリンダー温度240~260℃、金型温度50℃、冷却時間5分の条件で成形した。得られたプレートを目視観察し、以下の基準で評価した。
○:ヒケ及び反りは認められない。
×:ヒケ若しくは反り、又はヒケ及び反りが認められる Measuring method (1) Formability:
Using an injection molding machine with a clamping force of 120 tons, an injection molded plate with a length of 64.4 mm, a width of 64.4 mm, and a thickness of 3 mm is obtained under the conditions of a cylinder temperature of 240 to 260 ° C., a mold temperature of 50 ° C., and a cooling time of 5 minutes. Molded. The obtained plate was visually observed and evaluated according to the following criteria.
○: Sink and warp are not recognized.
X: Sink or warp, or sink and warp
ASTM D257規格(1987年版)に準拠し、二重リングプローブ法(リングプローブ法)により測定した。即ち、上記試験(1)の方法で得た射出成形プレートを試験片とし、温度23±2 ℃、相対湿度50±5%の試験室において40時間以上状態調整を行った後、株式会社三菱化学アナリテックの抵抗率計「ハイレスタ UP MCP-HT450型(商品名)」、株式会社三菱化学アナリテックの二重リングプローブ(リング形状は、主電極外径0.59cm、ガード電極内径1.1cm。)「URSプローブ(商品名)」、及び株式会社三菱化学アナリテックのレジテーブル「UFL(商品名」を使用し、印加電圧500V、測定時間60秒の条件で測定した。測定は1つの試験片について2箇所の測定位置において行い、これを3つの試験片について行い、合計6個の測定値の平均値を、このサンプルの体積抵抗率とした。
なお電気抵抗率測定方法及びその理論については、株式会社三菱化学アナリテックのホームページ(http://www.mccat.co.jp/3seihin/genri/ghlup2.htm)などを参照することができる。 (2) Volume resistivity (antistatic):
In accordance with the ASTM D257 standard (1987 version), the measurement was performed by the double ring probe method (ring probe method). That is, the injection molded plate obtained by the method of the above test (1) was used as a test piece, and after conditioning for 40 hours or more in a test room at a temperature of 23 ± 2 ° C. and a relative humidity of 50 ± 5%, Mitsubishi Chemical Corporation Analitech's resistivity meter “HIRESTA UP MCP-HT450 (trade name)”, Mitsubishi Chemical Analitech's double ring probe (ring shape: main electrode outer diameter 0.59 cm, guard electrode inner diameter 1.1 cm). ) Measured under the conditions of an applied voltage of 500 V and a measurement time of 60 seconds using a “URS probe (trade name)” and a register table “UFL (trade name)” of Mitsubishi Chemical Analytech Co., Ltd. Measurement was performed on one test piece. This was performed at two measurement positions, and this was performed for three test pieces. The average value of a total of six measurement values was taken as the volume resistivity of this sample.
In addition, about the electrical resistivity measurement method and its theory, the homepage (http://www.mccat.co.jp/3seihin/genri/ghlup2.html) of Mitsubishi Chemical Analytech Co., Ltd. can be referred.
上記試験(1)の方法で得た射出成形プレートを、25℃の蒸留水を充填した水槽中で、プレートの表面をガーゼ(川本産業株式会社の医療用タイプ1ガーゼ)で10分間洗浄し、清浄な紙で水分を拭き取った後、温度23±2 ℃、相対湿度50±5%の試験室にて24時間以上乾燥し、上記試験(2)の方法に従い体積抵抗率を測定した。 (3) Volume resistivity after washing with water (antistatic durability 1):
In the water tank filled with distilled water at 25 ° C., the surface of the injection molded plate obtained by the test (1) was washed with gauze (medical type 1 gauze from Kawamoto Sangyo Co., Ltd.) for 10 minutes, After wiping off moisture with clean paper, it was dried in a test room at a temperature of 23 ± 2 ° C. and a relative humidity of 50 ± 5% for 24 hours or more, and the volume resistivity was measured according to the method of test (2).
上記試験(1)の方法で得た射出成形プレートを、JIS L 0849の学振試験機に置き、学振試験機の摩擦端子に、4枚重ねのガーゼ(川本産業株式会社の医療用タイプ1ガーゼ)で覆ったステンレス板(縦10mm、横10mm、厚み1mm)を取付け、該ステンレス板の縦横面が試験片と接触するようにセットし、350g荷重を載せ、試験片を、摩擦端子の移動距離60mm、速度1往復/秒の条件で往復300回払拭した後、上記試験(2)の方法に従い、試験片の払拭箇所の体積抵抗率を測定した。 (4) Volume resistivity after wiping (anti-static durability 2):
The injection-molded plate obtained by the method of the above test (1) is placed on a Gakushin tester of JIS L 0849, and four layers of gauze (medical type 1 of Kawamoto Sangyo Co., Ltd.) is placed on the friction terminal of the Gakushin tester. Attach a stainless steel plate (length 10 mm, width 10 mm, thickness 1 mm) covered with gauze), set the stainless steel plate so that the vertical and horizontal surfaces are in contact with the test piece, place a 350 g load, and move the test piece to the friction terminal After wiping 300 times under the conditions of a distance of 60 mm and a speed of 1 reciprocation / second, the volume resistivity of the wiping location of the test piece was measured according to the method of test (2).
測定には、パーキンエルマー社の加熱脱着式ガスクロマトグラフ質量分析装置を使用した。
(5-1)加熱脱着法によるアウトガスの捕集:
樹脂組成物を冷凍粉砕して2mm角以下の粉砕物とし、上記で得た粉砕物0.1gを、上記装置の捕集ユニットのサンプルホルダに入れ、120℃で10分間加熱し、発生した揮発性物質を、キャリアガスとしてヘリウムガスを使用して、5℃に保たれた冷却トラップ管に捕集した。
(5-2)揮発性物質(アウトガス)の定量:
上記(5-1)で揮発性物質をトラップした冷却トラップ管を昇温速度40℃/秒で300℃まで加熱し、離脱するガスを上記装置のガスクロマトグラフ質量分析ユニットに供給し、その発生量を定量した。このとき標準サンプル(所定量のn-デカンを、ジーエルサイエンス株式会社の2,6‐ジフェニル‐パラ‐フェニレンオキサイドをベースにした弱極性のポーラスポリマービーズ吸着剤「TenaxTA(商品名)」に含浸させたもの)を用いて、上記の方法と同様に測定して作成した検量線を使用した。 (5) Outgas amount:
For the measurement, a heat desorption gas chromatograph mass spectrometer manufactured by PerkinElmer was used.
(5-1) Collection of outgas by thermal desorption method:
The resin composition is frozen and pulverized to obtain a pulverized product of 2 mm square or less, and 0.1 g of the pulverized product obtained above is placed in a sample holder of the collection unit of the above apparatus and heated at 120 ° C. for 10 minutes to generate generated volatilization. The substance was collected in a cold trap tube maintained at 5 ° C. using helium gas as the carrier gas.
(5-2) Determination of volatile substances (outgas):
The cooled trap tube trapped with the volatile substance in (5-1) above is heated to 300 ° C. at a heating rate of 40 ° C./sec, and the released gas is supplied to the gas chromatograph mass spectrometric unit of the above apparatus. Was quantified. At this time, a standard sample (a predetermined amount of n-decane was impregnated with “TenaxTA” (trade name), a weakly polar porous polymer bead adsorbent based on 2,6-diphenyl-para-phenylene oxide of GL Sciences Inc. And a calibration curve prepared by measurement in the same manner as described above was used.
型締め力120tonの射出成形機を使用し、縦60mm、横60mm、厚み0.5mmの射出成形シートを、シリンダー温度240~260℃、金型温度50℃、冷却時間5分の条件で成形し、得られた射出成形シートのヘーズを、JIS K 7136:2000に従い、日本電色工業株式会社の濁度計「NDH2000(商品名)」を用いて測定した。以下の基準で評価した。
◎:5%未満
○:5%以上50%未満
×:50%超 (6) Haze (transparency):
Using an injection molding machine with a clamping force of 120 tons, an injection molded sheet with a length of 60 mm, a width of 60 mm, and a thickness of 0.5 mm was molded under conditions of a cylinder temperature of 240 to 260 ° C, a mold temperature of 50 ° C, and a cooling time of 5 minutes. The haze of the obtained injection-molded sheet was measured according to JIS K 7136: 2000 using a turbidimeter “NDH2000 (trade name)” manufactured by Nippon Denshoku Industries Co., Ltd. Evaluation was made according to the following criteria.
◎: Less than 5% ○: 5% or more and less than 50%
×: Over 50%
ASTM D648-07に準拠し、型締め力120tonの射出成形機を使用し、シリンダー温度240~260℃、金型温度50℃、冷却時間5分の条件で成形した長さ127mm、高さ13mm、厚み6mmの試験片を用い、支点間距離100.0mm(B法)、荷重1.82MPa 、昇温速度2℃の条件で測定した。 (7) Thermal deformation temperature (heat resistance):
In accordance with ASTM D648-07, using an injection molding machine with a clamping force of 120 ton, a cylinder temperature of 240 to 260 ° C, a mold temperature of 50 ° C, a cooling time of 5 minutes, a length of 127mm, a height of 13mm, A test piece having a thickness of 6 mm was used, and measurement was performed under the conditions of a fulcrum distance of 100.0 mm (Method B), a load of 1.82 MPa, and a temperature increase rate of 2 ° C.
(A)ポリエステル系樹脂:
(A-1)多価カルボン酸に由来する構造単位の総和を100モル%として、テレフタル酸に由来する構造単位100モル%、多価オールに由来する構造単位の総和を100モル%として、1,4-シクロヘキサンジメタノールに由来する構造単位77モル%、及び2,2,4,4,-テトラメチル-1,3-シクロブタンジオールに由来する構造単位23モル%を含むポリエステル系樹脂。ガラス転移温度108℃、融解熱量0J/g(DSCセカンド融解曲線に明瞭な融解ピークなし)。
(A-2)多価カルボン酸に由来する構造単位の総和を100モル%として、テレフタル酸に由来する構造単位100モル%、多価オールに由来する構造単位の総和を100モル%として、1,4-シクロヘキサンジメタノールに由来する構成単位64モル%、及び2,2,4,4,-テトラメチル-1,3-シクロブタンジオールに由来する構成単位36モル%を含むポリエステル系樹脂。ガラス転移温度119℃、融解熱量0J/g(DSCセカンド融解曲線に明瞭な融解ピークなし)。 Raw material used (A) Polyester resin:
(A-1) The sum of structural units derived from polyvalent carboxylic acid is defined as 100 mol%, the structural unit derived from terephthalic acid is defined as 100 mol%, and the sum of structural units derived from polyvalent ol is defined as 100 mol%. Polyester resin containing 77 mol% of structural units derived from 1,4-cyclohexanedimethanol and 23 mol% of structural units derived from 2,2,4,4, -tetramethyl-1,3-cyclobutanediol. Glass transition temperature 108 ° C., heat of fusion 0 J / g (no clear melting peak in DSC second melting curve).
(A-2) The sum of the structural units derived from polyvalent carboxylic acid is defined as 100 mol%, the structural unit derived from terephthalic acid is defined as 100 mol%, and the sum of structural units derived from polyvalent ol is defined as 100 mol%. Polyester resin containing 64 mol% of structural units derived from 1,4-cyclohexanedimethanol and 36 mol% of structural units derived from 2,2,4,4, -tetramethyl-1,3-cyclobutanediol. Glass transition temperature 119 ° C., heat of fusion 0 J / g (no clear melting peak in DSC second melting curve).
(A’-1)多価カルボン酸に由来する構造単位の総和を100モル%として、テレフタル酸に由来する構造単位100モル%、多価オールに由来する構造単位の総和を100モル%として、1,4-シクロヘキサンジメタノールに由来する構造単位34モル%、及びエチレングリコールに由来する構造単位66モル%を含むポリエステル系樹脂。ガラス転移温度81℃、融解熱量0J/g(DSCセカンド融解曲線に明瞭な融解ピークなし)。
(A’-2)三菱エンジニアリングプラスチックス株式会社のポリカーボネート系樹脂「ユーピロン3000(商品名)」。ガラス転移温度143℃。 (A ′) Comparative resin:
(A′-1) The sum of structural units derived from polyvalent carboxylic acid is 100 mol%, the structural unit derived from terephthalic acid is 100 mol%, the sum of structural units derived from polyvalent ol is 100 mol%, A polyester resin comprising 34 mol% of structural units derived from 1,4-cyclohexanedimethanol and 66 mol% of structural units derived from ethylene glycol. Glass transition temperature 81 ° C., heat of fusion 0 J / g (no clear melting peak in DSC second melting curve).
(A'-2) Polycarbonate resin “Iupilon 3000 (trade name)” manufactured by Mitsubishi Engineering Plastics Co., Ltd. Glass transition temperature 143 ° C.
(B-1)特開平8-283548号公報の段落0063、参考例1の記載に従い、得たポリエーテルエステル樹脂。上記成分(b1)はジメチルテレフタレート、上記成分(b2)は5-ナトリウムスルホイソフタル酸ジメチル、上記成分(b3)はポリエチレングリコール(数平均分子量20000)、上記成分(b4)は1,4-ブタンジオール。上記成分(b1)に由来する構造単位の含有量と上記成分(b2)に由来する構造単位の含有量との和を100モル%として、上記成分(b1)に由来する構造単位75モル%、上記成分(b2)に由来する構造単位を25モル%。上記成分(b1)に由来する構造単位の含有量、上記成分(b2)に由来する構造単位の含有量、上記成分(b3)に由来する構造単位の含有量、及び上記成分(b4)に由来する構造単位の含有量の和を100質量%として、上記成分(b3)に由来する構造単位の含有量が11質量%。
(B-2)特開平8-283548号公報の段落0064、参考例2の記載に従い、得たポリエーテルエステル樹脂。上記成分(b1)はジメチルテレフタレート、上記成分(b2)は5-ナトリウムスルホイソフタル酸ジメチル、上記成分(b3)はポリエチレングリコール(数平均分子量20000)、上記成分(b4)は1,4-ブタンジオール。上記成分(b1)に由来する構造単位の含有量と上記成分(b2)に由来する構造単位の含有量との和を100モル%として、上記成分(b1)に由来する構造単位85モル%、上記成分(b2)に由来する構造単位を15モル%。上記成分(b1)に由来する構造単位の含有量、上記成分(b2)に由来する構造単位の含有量、上記成分(b3)に由来する構造単位の含有量、及び上記成分(b4)に由来する構造単位の含有量の和を100質量%として、上記成分(b3)に由来する構造単位の含有量20質量%。
(B-3)特開平8-283548号公報の段落0065、参考例3の記載に従い、得たポリエーテルエステル樹脂。上記成分(b1)はジメチルテレフタレート、上記成分(b2)は5-ナトリウムスルホイソフタル酸ジメチル、上記成分(b3)はポリエチレングリコール(数平均分子量20000)、上記成分(b4)は1,4-ブタンジオール。上記成分(b1)に由来する構造単位の含有量と上記成分(b2)に由来する構造単位の含有量との和を100モル%として、上記成分(b1)に由来する構造単位75モル%、上記成分(b2)に由来する構造単位を25モル%。上記成分(b1)に由来する構造単位の含有量、上記成分(b2)に由来する構造単位の含有量、上記成分(b3)に由来する構造単位の含有量、及び上記成分(b4)に由来する構造単位の含有量の和を100質量%として、上記成分(b3)に由来する構造単位の含有量20質量%。
(B-4)特開平8-283548号公報の段落0066、参考例4の記載に従い、得たポリエーテルエステル樹脂。上記成分(b1)はジメチルテレフタレート、上記成分(b2)は5-ナトリウムスルホイソフタル酸ジメチル、上記成分(b3)はポリエチレングリコール(数平均分子量4000)、上記成分(b4)は1,4-ブタンジオール。上記成分(b1)に由来する構造単位の含有量と上記成分(b2)に由来する構造単位の含有量との和を100モル%として、上記成分(b1)に由来する構造単位75モル%、上記成分(b2)に由来する構造単位を25モル%。上記成分(b1)に由来する構造単位の含有量、上記成分(b2)に由来する構造単位の含有量、上記成分(b3)に由来する構造単位の含有量、及び上記成分(b4)に由来する構造単位の含有量の和を100質量%として、上記成分(b3)に由来する構造単位の含有量20質量%。 (B) Polyetherester resin:
(B-1) A polyetherester resin obtained in accordance with the description in paragraph 0063 and Reference Example 1 of JP-A-8-283548. The component (b1) is dimethyl terephthalate, the component (b2) is dimethyl 5-sodium sulfoisophthalate, the component (b3) is polyethylene glycol (number average molecular weight 20000), and the component (b4) is 1,4-butanediol. . When the sum of the content of the structural unit derived from the component (b1) and the content of the structural unit derived from the component (b2) is 100 mol%, the structural unit derived from the component (b1) is 75 mol%, 25 mol% of structural units derived from the component (b2). Content of structural unit derived from component (b1), content of structural unit derived from component (b2), content of structural unit derived from component (b3), and derived from component (b4) The content of the structural unit derived from the component (b3) is 11% by mass, where the sum of the content of the structural unit is 100% by mass.
(B-2) A polyetherester resin obtained in accordance with the description in paragraph 0064 and Reference Example 2 of JP-A-8-283548. The component (b1) is dimethyl terephthalate, the component (b2) is dimethyl 5-sodium sulfoisophthalate, the component (b3) is polyethylene glycol (number average molecular weight 20000), and the component (b4) is 1,4-butanediol. . When the sum of the content of the structural unit derived from the component (b1) and the content of the structural unit derived from the component (b2) is 100 mol%, the structural unit derived from the component (b1) is 85 mol%, 15 mol% of structural units derived from the component (b2). Content of structural unit derived from component (b1), content of structural unit derived from component (b2), content of structural unit derived from component (b3), and derived from component (b4) The content of the structural unit derived from the component (b3) is 20% by mass, where the sum of the content of the structural unit is 100% by mass.
(B-3) A polyetherester resin obtained according to the description in paragraph 0065 and Reference Example 3 of JP-A-8-283548. The component (b1) is dimethyl terephthalate, the component (b2) is dimethyl 5-sodium sulfoisophthalate, the component (b3) is polyethylene glycol (number average molecular weight 20000), and the component (b4) is 1,4-butanediol. . When the sum of the content of the structural unit derived from the component (b1) and the content of the structural unit derived from the component (b2) is 100 mol%, the structural unit derived from the component (b1) is 75 mol%, 25 mol% of structural units derived from the component (b2). Content of structural unit derived from component (b1), content of structural unit derived from component (b2), content of structural unit derived from component (b3), and derived from component (b4) The content of the structural unit derived from the component (b3) is 20% by mass, where the sum of the content of the structural unit is 100% by mass.
(B-4) A polyetherester resin obtained in accordance with the description in paragraph 0066 and Reference Example 4 of JP-A-8-283548. The component (b1) is dimethyl terephthalate, the component (b2) is dimethyl 5-sodium sulfoisophthalate, the component (b3) is polyethylene glycol (number average molecular weight 4000), and the component (b4) is 1,4-butanediol. . When the sum of the content of the structural unit derived from the component (b1) and the content of the structural unit derived from the component (b2) is 100 mol%, the structural unit derived from the component (b1) is 75 mol%, 25 mol% of structural units derived from the component (b2). Content of structural unit derived from component (b1), content of structural unit derived from component (b2), content of structural unit derived from component (b3), and derived from component (b4) The content of the structural unit derived from the component (b3) is 20% by mass, where the sum of the content of the structural unit is 100% by mass.
(B’-1)三洋化成株式会社のポリエーテルエステルアミド樹脂「ペレスタット6321NC(商品名)」。スルホン酸塩基で置換された芳香族多価カルボン酸に由来する構造単位を有しない。 (B ′) Comparative polyetherester resin:
(B′-1) A polyether ester amide resin “Pelestat 6321NC (trade name)” manufactured by Sanyo Chemical Co., Ltd. There is no structural unit derived from an aromatic polyvalent carboxylic acid substituted with a sulfonate group.
(C-1)関東化学株式会社のドデシルベンゼンスルホン酸ナトリウム。 (C) Ionic surfactant (C-1) Sodium dodecylbenzenesulfonate from Kanto Chemical Co., Inc.
20mmφの同方向二軸混練機を使用し、表1~3の何れか1に示す配合比の配合物を、設定温度240~260℃で溶融混練し、樹脂組成物を得た。上記試験(1)~(7)を行った。結果を表1~3の何れか1に示す。 Examples 1-11, Examples 1C-7C
Using a 20 mmφ same-direction biaxial kneader, a blend having a blending ratio shown in any one of Tables 1 to 3 was melt-kneaded at a preset temperature of 240 to 260 ° C. to obtain a resin composition. The above tests (1) to (7) were conducted. The results are shown in any one of Tables 1 to 3.
Claims (6)
- (A)下記特性(a1)、及び(a2)を有するポリエステル系樹脂 100質量部;及び、
(B)スルホン酸塩基で置換された芳香族多価カルボン酸に由来する構造単位を有するポリエーテルエステル樹脂 7~25質量部;
を含む制電性樹脂組成物。
(a1)多価カルボン酸に由来する構造単位の総和を100モル%として、テレフタル酸に由来する構造単位90~100モル%、及びイソフタル酸に由来する構造単位10~0モル%を含む。
(a2)多価オールに由来する構造単位の総和を100モル%として、1,4-シクロヘキサンジメタノールに由来する構造単位50~90モル%、及び2,2,4,4,-テトラメチル-1,3-シクロブタンジオールに由来する構造単位50~10モル%を含む。 (A) 100 parts by mass of a polyester-based resin having the following characteristics (a1) and (a2); and
(B) 7 to 25 parts by mass of a polyetherester resin having a structural unit derived from an aromatic polyvalent carboxylic acid substituted with a sulfonate group;
An antistatic resin composition comprising:
(A1) The total of structural units derived from polyvalent carboxylic acid is 100 mol%, and includes 90 to 100 mol% of structural units derived from terephthalic acid and 10 to 0 mol% of structural units derived from isophthalic acid.
(A2) 50 to 90 mol% of structural units derived from 1,4-cyclohexanedimethanol, and 2,2,4,4, -tetramethyl- when the total of structural units derived from polyvalent ol is 100 mol% It contains 50 to 10 mol% of structural units derived from 1,3-cyclobutanediol. - 上記成分(B)が、
(b1)テレフタル酸、2,6-ナフタレンジカルボン酸、2,7-ナフタレンジカルボン酸、ビフェニル-4,4’-ジカルボン酸、及びこれらのエステル形成性誘導体からなる群から選択される1種以上の芳香族ジカルボン酸に由来する構造単位;
(b2)下記式(1)で表される、スルホン酸塩基で置換された芳香族多価カルボン酸及び/又はそのエステル形成性誘導体に由来する構造単位;
(b3)数平均分子量200~50000のポリアルキレングリコールに由来する構造単位;及び、
(b4)炭素数2~10のグリコールに由来する構造単位;
を含み、
ここで上記成分(b1)に由来する構造単位の含有量と上記成分(b2)に由来する構造単位の含有量との和を100モル%として、
上記成分(b1)に由来する構造単位を98~70モル%、
上記成分(b2)に由来する構造単位を2~30モル%となる量で含み;
上記成分(b1)に由来する構造単位の含有量、上記成分(b2)に由来する構造単位の含有量、上記成分(b3)に由来する構造単位の含有量、及び上記成分(b4)に由来する構造単位の含有量の和を100質量%として、
上記成分(b3)に由来する構造単位の含有量が10~60質量%である;
ポリエーテルエステル樹脂である
請求項1に記載の制電性樹脂組成物。
Arは少なくとも3つの水素原子が置換された芳香環構造を有する基;
R1及びR2はそれぞれ独立に水素原子、炭素数1~6のアルキル基又は炭素数6~12のアリール基;
M+は金属イオン、テトラアルキルホスホニウムイオン又はテトラアルキルアンモニウムイオンを表す。 The component (B) is
(B1) one or more selected from the group consisting of terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, and ester-forming derivatives thereof Structural units derived from aromatic dicarboxylic acids;
(B2) a structural unit derived from an aromatic polyvalent carboxylic acid substituted with a sulfonate group and / or an ester-forming derivative thereof, represented by the following formula (1);
(B3) a structural unit derived from a polyalkylene glycol having a number average molecular weight of 200 to 50,000;
(B4) a structural unit derived from a glycol having 2 to 10 carbon atoms;
Including
Here, assuming that the sum of the content of the structural unit derived from the component (b1) and the content of the structural unit derived from the component (b2) is 100 mol%,
98 to 70 mol% of structural units derived from the component (b1),
Containing structural units derived from the component (b2) in an amount of 2 to 30 mol%;
Content of structural unit derived from component (b1), content of structural unit derived from component (b2), content of structural unit derived from component (b3), and derived from component (b4) The sum of the content of structural units to be 100% by mass
The content of structural units derived from the component (b3) is 10 to 60% by mass;
The antistatic resin composition according to claim 1, which is a polyether ester resin.
Ar is a group having an aromatic ring structure in which at least three hydrogen atoms are substituted;
R1 and R2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms;
M + represents a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion. - 更に(C)イオン性界面活性剤を、上記成分(A)100質量部に対して、0.5~5質量部含有する請求項1又は2に記載の制電性樹脂組成物。 The antistatic resin composition according to claim 1 or 2, further comprising (C) 0.5 to 5 parts by mass of an ionic surfactant with respect to 100 parts by mass of the component (A).
- 体積抵抗率が10の9乗~10の10乗Ω・cmである請求項1~3の何れか1項に記載の制電性樹脂組成物。 4. The antistatic resin composition according to claim 1, having a volume resistivity of 10 9 to 10 10 Ω · cm.
- 請求項1~4の何れか1項に記載の制電性樹脂組成物を含む物品。 An article comprising the antistatic resin composition according to any one of claims 1 to 4.
- 請求項1~4の何れか1項に記載の制電性樹脂組成物を含む精密電子機器。 A precision electronic device comprising the antistatic resin composition according to any one of claims 1 to 4.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017532555A JP6656253B2 (en) | 2015-08-05 | 2016-07-28 | Antistatic resin composition |
KR1020187005460A KR102513777B1 (en) | 2015-08-05 | 2016-07-28 | antistatic resin composition |
CN201680044661.1A CN107849340B (en) | 2015-08-05 | 2016-07-28 | Antistatic resin composition |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015154830 | 2015-08-05 | ||
JP2015-154830 | 2015-08-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017022637A1 true WO2017022637A1 (en) | 2017-02-09 |
Family
ID=57943028
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2016/072211 WO2017022637A1 (en) | 2015-08-05 | 2016-07-28 | Antistatic resin composition |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP6656253B2 (en) |
KR (1) | KR102513777B1 (en) |
CN (1) | CN107849340B (en) |
TW (1) | TWI715604B (en) |
WO (1) | WO2017022637A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019019322A (en) * | 2017-07-14 | 2019-02-07 | 花王株式会社 | Manufacturing method of thermoplastic resin composition |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2022064949A1 (en) * | 2020-09-24 | 2022-03-31 | ||
CN114437518B (en) * | 2021-12-29 | 2023-11-24 | 金发科技股份有限公司 | Low-warpage glass fiber reinforced PBT composition and preparation method and application thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006127831A1 (en) * | 2005-05-26 | 2006-11-30 | Eastman Chemical Company | Miscible high tg polyester/polymer blend compositions and films formed therefrom |
JP2009001618A (en) * | 2007-06-19 | 2009-01-08 | Riken Technos Corp | Antistatic polyester resin composition |
WO2014061429A1 (en) * | 2012-10-15 | 2014-04-24 | 旭化成ケミカルズ株式会社 | Thermoplastic resin composition and molded product thereof |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62230835A (en) | 1986-03-31 | 1987-10-09 | Takemoto Oil & Fat Co Ltd | Antistatic agent for synthetic polymer |
JPH0745612B2 (en) | 1986-05-20 | 1995-05-17 | 東レ株式会社 | Thermoplastic resin composition |
JPH078954B2 (en) | 1990-03-05 | 1995-02-01 | 旭化成工業株式会社 | Thermoplastic resin composition and antistatic molding using the same |
EP0519314B1 (en) | 1991-06-20 | 1997-02-05 | The B.F. Goodrich Company | Chain extended low molecular weight polyethylene glycols as electrostatic dissipating agents in polymer blend compositions |
JP3132854B2 (en) | 1991-10-08 | 2001-02-05 | ダイセル化学工業株式会社 | Polymeric antistatic agent |
JPH0715025B2 (en) | 1992-02-12 | 1995-02-22 | 日鉱石油化学株式会社 | Antistatic agent for synthetic resin |
JPH0657153A (en) | 1992-08-10 | 1994-03-01 | Daicel Chem Ind Ltd | Antistatic resin composition |
JPH0789720A (en) * | 1993-06-30 | 1995-04-04 | Asahi Glass Co Ltd | Coating liquid for colored film forming, colored film, colored antistatic film and colored low reflective antistatic film |
JP3621757B2 (en) | 1994-07-13 | 2005-02-16 | 帝人化成株式会社 | Permanent antistatic resin composition |
JPH08112866A (en) * | 1994-10-17 | 1996-05-07 | Sony Chem Corp | Hard coat film and manufacture thereof |
JP3399767B2 (en) | 1997-02-13 | 2003-04-21 | 帝人株式会社 | Permanent antistatic polycarbonate film or sheet and method for producing them |
BR9916355A (en) * | 1998-12-18 | 2001-09-11 | Eastman Chem Co | Copolyester composition, shaped article, and process for the manufacture of a polyester composition |
US7235623B2 (en) * | 2003-11-26 | 2007-06-26 | Eastman Chemical Company | Polyester compositions for calendering |
JP4565622B2 (en) | 2004-07-09 | 2010-10-20 | 帝人化成株式会社 | Polyester composition |
JP2006077217A (en) * | 2004-09-13 | 2006-03-23 | Sanyo Chem Ind Ltd | Reactive antistatic agent |
US8063172B2 (en) * | 2005-06-17 | 2011-11-22 | Eastman Chemical Company | Film(s) and/or sheet(s) made using polyester compositions containing low amounts of cyclobutanediol |
CN101555636A (en) * | 2008-04-09 | 2009-10-14 | 东丽纤维研究所(中国)有限公司 | Antistatic polyester fiber |
-
2016
- 2016-07-28 JP JP2017532555A patent/JP6656253B2/en active Active
- 2016-07-28 CN CN201680044661.1A patent/CN107849340B/en active Active
- 2016-07-28 WO PCT/JP2016/072211 patent/WO2017022637A1/en active Application Filing
- 2016-07-28 KR KR1020187005460A patent/KR102513777B1/en active IP Right Grant
- 2016-08-04 TW TW105124789A patent/TWI715604B/en active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006127831A1 (en) * | 2005-05-26 | 2006-11-30 | Eastman Chemical Company | Miscible high tg polyester/polymer blend compositions and films formed therefrom |
JP2009001618A (en) * | 2007-06-19 | 2009-01-08 | Riken Technos Corp | Antistatic polyester resin composition |
WO2014061429A1 (en) * | 2012-10-15 | 2014-04-24 | 旭化成ケミカルズ株式会社 | Thermoplastic resin composition and molded product thereof |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019019322A (en) * | 2017-07-14 | 2019-02-07 | 花王株式会社 | Manufacturing method of thermoplastic resin composition |
JP7148301B2 (en) | 2017-07-14 | 2022-10-05 | 花王株式会社 | Method for producing thermoplastic resin composition |
US11603434B2 (en) | 2017-07-14 | 2023-03-14 | Kao Corporation | Method for manufacturing thermoplastic resin composition |
Also Published As
Publication number | Publication date |
---|---|
KR20180037214A (en) | 2018-04-11 |
JP6656253B2 (en) | 2020-03-04 |
JPWO2017022637A1 (en) | 2018-06-07 |
TW201718760A (en) | 2017-06-01 |
TWI715604B (en) | 2021-01-11 |
CN107849340A (en) | 2018-03-27 |
CN107849340B (en) | 2020-08-04 |
KR102513777B1 (en) | 2023-03-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7067186B2 (en) | Thermoplastic resin composition | |
WO2017022637A1 (en) | Antistatic resin composition | |
US20120128984A1 (en) | Polyester resin composition | |
US8030388B2 (en) | Vibration-damping material | |
JP2011132293A (en) | Thermoplastic elastomer resin composition for substrate storage container gasket and gasket molded product for substrate storage container | |
JP2019131726A (en) | Antistatic resin composition | |
JP4631134B2 (en) | Flame-retardant polyester resin for adhesive and adhesive | |
JP2003003058A (en) | Antistatic agent composition for thermoplastic resin and antistatic thermoplastic resin composition | |
JP2009001618A (en) | Antistatic polyester resin composition | |
JP2000072960A (en) | Polyester copolymer composition for housing | |
JP3399767B2 (en) | Permanent antistatic polycarbonate film or sheet and method for producing them | |
JP2008150442A (en) | Coating composition, laminate and flexible flat cable | |
JPH08283548A (en) | Permanently antistatic resin composition | |
JPH09194714A (en) | Silicon wafer carrier having permanent antistatic property | |
US20200377649A1 (en) | Polyester elastomer resin composition | |
JP6866234B2 (en) | Polycarbonate resin composition | |
JP2000072959A (en) | Polyester resin composition for housing | |
JP2000044778A (en) | Resin composition and component for upset-detecting switch made of the same | |
JP3592834B2 (en) | Resin composition imparting permanent antistatic properties and thermoplastic resin composition containing the same | |
JP5322409B2 (en) | Method for preparing antistatic thermoplastic resin composition, antistatic thermoplastic resin composition, and antistatic thermoplastic resin molded article | |
JP2001089750A (en) | Antistatic agent and transparent antistatic resin composition | |
JP3574705B2 (en) | Permanent antistatic resin composition and method for producing the same | |
WO2023153181A1 (en) | Antistatic film | |
WO2023153180A1 (en) | Antistatic film | |
TWI627228B (en) | Resin composition for packaging electric and electronic parts, manufacturing method of electric and electronic part package, and electric and electronic part package |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16832916 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2017532555 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20187005460 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 16832916 Country of ref document: EP Kind code of ref document: A1 |