CN107849340B - Antistatic resin composition - Google Patents
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- CN107849340B CN107849340B CN201680044661.1A CN201680044661A CN107849340B CN 107849340 B CN107849340 B CN 107849340B CN 201680044661 A CN201680044661 A CN 201680044661A CN 107849340 B CN107849340 B CN 107849340B
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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
- 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
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- 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
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- 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
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- 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
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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
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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Abstract
The invention provides an antistatic resin composition which is excellent in antistatic property, particularly in antistatic persistence, heat resistance and transparency and free from the problem of gas emission. The antistatic resin composition comprises 100 parts by mass of a polyester resin (A) having the following characteristics (a1) and (a2) and 7 to 25 parts by mass of a polyether ester resin (B) having a structural unit derived from an aromatic polycarboxylic acid substituted with a sulfonate group. (a1) The total of the structural units derived from the polycarboxylic acid is defined as 100 mol%, and the total of the structural units derived from the polycarboxylic acid contains 90 to 100 mol% of the structural unit derived from terephthalic acid and 0 to 10 mol% of the structural unit derived from isophthalic acid. (a2) The total of the structural units derived from the polyol is defined as 100 mol%, and the structural units derived from 1, 4-cyclohexanedimethanol comprise 50 to 90 mol% and 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol comprise 10 to 50 mol%.
Description
Technical Field
The present invention relates to an antistatic resin composition. More particularly, it relates to a polyester resin composition having antistatic properties.
Background
Since a precision electronic component such as a semiconductor wafer, a semiconductor element, an integrated circuit, or the like may be damaged due to a slight amount of charge (so-called electrostatic destruction), a material used for a tray, a packaging material, a storage tool, an outer package, or the like for transporting the precision electronic component is required to have a volume resistance value of 109～1010Omega cm. The packaging material is required to have transparency (haze value of 50% or less) to the extent that the presence of the content can be visually confirmed at least, and preferably to have transparency to the extent that product inspection can be visually performed and identification marks attached to the content can be confirmedGood haze (haze value of 15% or less). Further, heat resistance is required to cope with the following cases: heat generated in a drying process or the like when manufacturing a precision electronic component; heat generated in the drying step when manufacturing an article in which a precision electronic component is assembled; environmental temperature during transportation, storage, and actual use of precision electronic equipment (articles in which precision electronic components are assembled), for example, in-vehicle equipment such as audio equipment and information communication equipment; and the heat generated during the operation of the above-mentioned machine, heat resistance at a temperature of at least 80 ℃ is required.
Since thermoplastic resins have many excellent characteristics, many proposals have been made for setting the volume resistance value of thermoplastic resins to 109～1010The technique of Ω · cm has been put into practical use so that it can be applied to the field of precision electronic parts regardless of whether it is a material having high electrical insulation.
As the above-mentioned techniques, for example, resin compositions of a thermoplastic resin and an ionic surfactant such as an alkylsulfonate or an alkylbenzenesulfonate, particularly a surfactant such as an alkyl (aryl) sulfonate, have been proposed (for example, patent documents 1 and 2). However, this technique reduces the resistance value by bleeding a low molecular weight surfactant from the surface of the molded article, and therefore has a problem that the surfactant on the surface is wiped or washed with water to reduce the antistatic property (increase the resistance value) and generate outgas.
As the above-mentioned techniques, for example, there have been proposed resin compositions containing a thermoplastic resin having antistatic properties (for example, polyetheresteramide (patent document 3), a graft polymer in which a main chain copolymer is composed of a polyamide and a branched polymer is composed of a block polymer of a polyalkylene ether and a thermoplastic polyester (patent document 4), a specific polyamideimide elastomer (patent document 5), a reaction product of a specific polyethylene glycol, a specific non-hindered diisocyanate, and a specific aliphatic chain extender ethylene glycol (patent document 6), and the like). However, in these techniques, in order to obtain sufficient antistatic properties, it is sometimes necessary to blend a large amount of a thermoplastic resin having antistatic properties. Further, heat resistance and transparency thereof cannot be satisfied. Further, these antistatic thermoplastic resins have properties of promoting the deterioration of polyester resins and reducing the molecular weight, and resin compositions of polyester resins and these antistatic thermoplastic resins have a problem that molding defects such as burrs and sink marks are liable to occur in injection molded articles, for example.
Further, as the thermoplastic resin having the antistatic property, there have been proposed polyether esters (for example, polyether esters obtained by condensing a poly (oxyalkylene) diol having a specific molecular weight, a diol having 2 to 8 carbon atoms, a polycarboxylic acid having 4 to 20 carbon atoms, and the like (patent document 7), polyether esters obtained by polycondensing a poly (oxyalkylene) diol having a specific molecular weight, and a diol having 4 to 10 carbon atoms, such as an aromatic dicarboxylic acid having 4 to 20 carbon atoms, and the like (patent document 8), polyether esters obtained by polycondensing a poly (oxyalkylene) diol having a specific molecular weight, and a diol having 2 to 10 carbon atoms, such as an aromatic dicarboxylic acid having 4 to 20 carbon atoms, a poly (oxyalkylene) diol having a specific molecular weight, and a diol having 4 to 10 carbon atoms, such as a specific sulfonate group-containing a specific amount of an aromatic dicarboxylic acid (patent document 9), and polyether esters obtained by polycondensing a poly (oxyalkylene) diol having 4 to 10 carbon atoms, such. However, the antistatic properties of the polyetheresters alone are insufficient.
Therefore, it has been proposed to use an ionic surfactant (for example, paragraph 0031 of patent document 7, patent document 11) at the same time, but these techniques have problems of lowering of antistatic property due to water washing and wiping and generation of off-gas.
Therefore, patent document 12 proposes to use a polyester-based resin as a base resin, which is crystallized from a molten state for half an hour or more for at least 5 minutes. However, the base resin is not high in heat resistance due to such characteristics.
An antistatic resin composition which is excellent in antistatic properties, particularly in the persistence of antistatic properties, heat resistance and transparency and which does not have the problem of gas emission has not been proposed.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 5-222241
Patent document 2: japanese laid-open patent publication No. 62-230835
Patent document 3: japanese laid-open patent publication No. 62-273252
Patent document 4: japanese laid-open patent publication No. 5-97984
Patent document 5: japanese laid-open patent publication No. 3-255161
Patent document 6: japanese laid-open patent publication No. 5-222289
Patent document 7: japanese laid-open patent publication No. 6-57153
Patent document 8: japanese laid-open patent publication No. 8-283548
Patent document 9: japanese laid-open patent publication No. 10-219095
Patent document 10: japanese laid-open patent publication No. 2006-022232
Patent document 11: japanese laid-open patent publication No. 8-283548
Patent document 12: japanese laid-open patent publication No. 2009-001618
Disclosure of Invention
The invention provides an antistatic resin composition which is excellent in antistatic property, particularly in antistatic persistence, heat resistance and transparency and free from the problem of gas emission. Another object of the present invention is to provide the following antistatic resin composition: volume resistivity of 109～1010Omega cm, even if washing, wiping can maintain the antistatic properties, heat resistance, transparency and formability excellent, and does not have the gas emission problem.
The present inventors have earnestly studied and found that the above object can be achieved by a resin composition comprising a specific polyester-based resin and a specific polyether ester.
Namely, the antistatic resin composition of the present invention comprises:
100 parts by mass of a polyester-based resin (A) having the following characteristics (a1) and (a 2); and
7 to 25 parts by mass of a polyether ester resin (B) having a structural unit derived from a sulfonate group-substituted aromatic polycarboxylic acid,
(a1) the total of the structural units derived from the polycarboxylic acid is defined as 100 mol%, and the total of the structural units derived from the polycarboxylic acid is defined to contain 90 to 100 mol% of the structural unit derived from terephthalic acid and 0 to 10 mol% of the structural unit derived from isophthalic acid,
(a2) the total of the structural units derived from the polyol is defined as 100 mol%, and the structural units derived from 1, 4-cyclohexanedimethanol comprise 50 to 90 mol% and 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol comprise 10 to 50 mol%.
The second invention is the antistatic resin composition according to the first invention, the component (B) is a polyetherester resin comprising:
a structural unit derived from at least one aromatic dicarboxylic acid (b1) 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;
a structural unit derived from an aromatic polycarboxylic acid substituted with a sulfonate group and/or an ester-forming derivative thereof (b2) represented by the following chemical formula (1);
a structural unit derived from a polyalkylene glycol (b3) having a number average molecular weight of 200 to 50000; and
a structural unit derived from a C2-10 diol (b4),
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 defined as 100 mol%, and the sum includes 70 to 98 mol% of the structural unit derived from the component (b1) and 2 to 30 mol% of the structural unit derived from the component (b2),
the content of the structural unit derived from the component (b3) is 10 to 60% by mass, assuming that the sum of 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 content of the structural unit derived from the component (b4) is 100% by mass.
Chemical formula 1
In the chemical formula 1, the first and second,
ar represents a group having an aromatic ring structure substituted for at least three hydrogen atoms;
r1 and R2 each independently represent 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 tetraalkyl phosphonium ion or a tetraalkyl ammonium ion.
Third invention according to the first or second invention of the antistatic resin composition, relative to 100 parts by mass of the component (A), also contains 0.5 to 5 parts by mass of ionic surfactant (C).
Fourth invention the antistatic resin composition according to any one of the first to third inventions, which has a volume resistivity of 109～1010Ω·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 is excellent in antistatic properties, particularly in antistatic durability, heat resistance and transparency, and is free from the problem of gas emission. As a preferred antistatic resin composition of the present invention, the volume resistivity is 109～1010Omega cm, even if washing, wiping can maintain the antistatic properties, heat resistance, transparency and formability excellent, and does not have the gas emission problem. The resin composition can be used as a tray for transporting precision electronic components such as semiconductor wafers, semiconductor elements, and integrated circuits, a packaging material, a material for housing storage tools, exterior members, and the like, exterior members for precision electronic devices incorporating precision electronic components, and the like.
Drawings
FIG. 1 shows a polyester resin1Examples of H-NMR measurement.
Detailed Description
The antistatic resin composition comprises 100 parts by mass of a polyester resin (A) having the following characteristics (a1) and (a2) and 7 to 25 parts by mass of a polyether ester resin (B) having a structural unit derived from an aromatic polycarboxylic acid substituted with a sulfonate group.
(a1) The total of the structural units derived from the polycarboxylic acid is defined as 100 mol%, and the total of the structural units derived from the polycarboxylic acid contains 90 to 100 mol% of the structural unit derived from terephthalic acid and 0 to 10 mol% of the structural unit derived from isophthalic acid.
(a2) The total of the structural units derived from the polyol is defined as 100 mol%, and the structural units derived from 1, 4-cyclohexanedimethanol comprise 50 to 90 mol% and 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol comprise 10 to 50 mol%.
(A) Polyester-based resin:
the component (A) is a polyester resin and comprises (a1) 90 to 100 mol% of a structural unit derived from terephthalic acid and 0 to 10 mol% of a structural unit derived from isophthalic acid, with the total of the structural units derived from polycarboxylic acids being 100 mol%; (a2) the total of the structural units derived from the polyol is defined as 100 mol%, and the structural units derived from 1, 4-cyclohexanedimethanol include 50 to 90 mol%, preferably 55 to 85 mol%, and more preferably 60 to 80 mol%, and the structural units derived from 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol 10 to 50 mol%, preferably 15 to 45 mol%, and more preferably 20 to 40 mol%. Wherein the polycarboxylic acid comprises an ester-forming derivative thereof. That is, terephthalic acid comprises its ester-forming derivatives. Likewise, isophthalic acid comprises its ester-forming derivatives. Wherein the polyol comprises an ester-forming derivative thereof. That is, 1, 4-cyclohexanedimethanol comprises ester-forming derivatives thereof. Likewise, 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol comprises its ester-forming derivatives.
The component (a) may contain a structural unit derived from a polycarboxylic acid other than terephthalic acid and isophthalic acid as far as the object of the present invention is not concerned. Examples of the other polycarboxylic acids include aromatic polycarboxylic acids such as phthalic acid, naphthalenedicarboxylic acid, diphenyl-4, 4' -dicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenyl-3, 3' -dicarboxylic acid, diphenyl-4, 4' -dicarboxylic acid, and anthracenedicarboxylic acid; alicyclic polycarboxylic acids such as 1, 2-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid and 1, 4-cyclohexanedicarboxylic acid; aliphatic polycarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid; and ester-forming derivatives thereof, and the like. As the other polycarboxylic acids, one or more of them can be used.
The component (a) may contain, as far as the object of the present invention is not concerned, a structural unit derived from a polyol other than 1, 4-cyclohexanedimethanol and 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol. Examples of the other polyhydric alcohols include aliphatic polyhydric alcohols such as 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, dodecanediol, 3-methyl-1, 5-pentanediol, 2-methyl-1, 3-propanediol, 1, 2-cyclohexanediol, 1, 4-cyclohexanediol, glycerol, and trimethylolpropane; aromatic polyols such as xylene glycol, 4' -dihydroxybiphenyl, 2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bisphenol a, and alkylene oxide adducts of bisphenol a; and ester-forming derivatives thereof, and the like. As the polyol, one or more of them can be used.
The antistatic resin composition of the present invention has excellent heat resistance because the glass transition temperature of the component (a) is high (usually 90 ℃ or higher, preferably 100 ℃ or higher, and more preferably 110 ℃ or higher). Further, the component (a) is highly transparent, has non-crystallinity or low crystallinity, and is well mixed with the component (B), and therefore, the antistatic resin composition of the present invention is excellent in transparency.
In the present specification, a polyester-based resin having a second melting curve (melting curve measured in the last temperature rise process) measured by the following temperature program, in which the heat of fusion is 10J/g or less, is defined as amorphous, and a polyester-based resin exceeding 10J/g and 60J/g or less is defined as low crystalline, is defined as amorphous, using a Diamond DSC type differential scanning calorimeter of perkin elmer: the sample is kept at 320 ℃ for 5 minutes, then cooled to-50 ℃ at the cooling rate of 20 ℃/minute, kept at-50 ℃ for 5 minutes, and then heated to 320 ℃ at the heating rate of 20 ℃/minute.
In the present specification, a glass transition temperature at an intermediate point calculated according to a chart of fig. 2 of ASTM D3418 is defined as a glass transition temperature in a curve obtained by measuring a final temperature rise process of the following temperature program using a Diamond DSC type differential scanning calorimeter of perkin elmer corporation: the sample is heated to 200 ℃ at a heating rate of 50 ℃/min, is cooled to 50 ℃ at a cooling rate of 20 ℃/min after being kept at 200 ℃ for 10 min, and is heated to 200 ℃ at a heating rate of 20 ℃/min after being kept at 50 ℃ for 10 min.
Can use13C-NMR、1The ratio of the structural units derived from each component in the polyester-based resin was determined by H-NMR. In FIG. 1 is shown1Examples of H-NMR measurement.
For example, 20mg of the sample may be dissolved in chloroform-d1In a solvent of 0.6m L, a 125MHz NMR apparatus was used, and the measurement was carried out under the following conditions13C-NMR spectrum.
Chemical shift standard chloroform-d1：77ppm
Measurement mode monopulse proton broadband decoupling
Pulse width 45 ° (5.00 μ sec)
Number of points 64K
Observation range 250ppm (-25 to 225ppm)
Repeat time 5.5 seconds
Cumulative number of times 256
The measurement temperature was 23 deg.C
Window function exponential (BF: 1.0Hz)
For example, 20mg of the sample may be dissolved in chloroform-d1In a solvent of 0.6m L, a nuclear magnetic resonance apparatus of 400MHz was used, and the measurement was carried out under the following conditions1H-NMR spectrum.
Chemical shift standard chloroform: 7.24ppm
Measurement mode monopulse
Pulse width 45 ° (5.14 μ sec)
Number of points 16k
The measurement range is 15ppm (-2.5 to 12.5ppm)
Repetition time 7.8 seconds
Cumulative number of times of 64
The measurement temperature was 23 deg.C
Window function exponential (BF: 0.18Hz)
The peak assignment was carried out with reference to "pages 496 to 503 of the handbook for Polymer analysis (first print on 20. th. 9.2008, edited by society of society, Japan society of analytical chemistry, Polymer analysis research, Ltd.)", "independent administrative statue substance, NMR database of Material information station of Material research institute (http:// polymer. nims. go. jp/NMR /)"), and the ratio of each component in the component (a) was calculated from the peak area ratio. The analysis may be carried out by an analysis organization such as Mitsui chemical analysis center13C-NMR、1Measurement of H-NMR.
(B) Polyether ester resin:
the component (B) is a polyetherester resin having a structural unit derived from an aromatic polycarboxylic acid substituted with a sulfonate group. From the viewpoint of antistatic properties and transparency, the component (B) preferably comprises:
a structural unit derived from at least one aromatic dicarboxylic acid (b1) 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;
a structural unit derived from an aromatic polycarboxylic acid substituted with a sulfonate group and/or an ester-forming derivative thereof (b2) represented by the following chemical formula (1);
a structural unit derived from a polyalkylene glycol (b3) having a number average molecular weight of 200 to 50000; and the number of the first and second groups,
a structural unit derived from a C2-10 diol (b4),
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 content of the structural unit derived from the component (b3) is 10 to 60 mass% 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 mass%, and 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 content of the structural unit derived from the component (b4) is 100 mass%.
Chemical formula 1
In the chemical formula (1), Ar represents a group having an aromatic ring structure in which at least three hydrogen atoms are substituted, R1 and R2 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and M+Represents a metal ion, a tetraalkyl phosphonium ion or a tetraalkyl ammonium ion.
It is preferable that the component (B) contains a structural unit derived from at least one aromatic dicarboxylic acid (B1) 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, because heat resistance is further improved.
When the component (B) contains a structural unit derived from an aromatic polycarboxylic acid substituted with a sulfonate group and/or an ester-forming derivative thereof (B2) represented by the above chemical formula (1), the antistatic property is more excellent, and therefore, it is a preferable embodiment.
For Ar in the above chemical formula (1), Ar is a group having an aromatic ring structure substituted for at least three hydrogen atoms. As Ar in the above chemical formula (1), for example, 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 are cited. The substituent(s) may be substituted by not only three hydrogen atoms but also one or more hydrogen atoms with a substituent(s) such as an alkyl group, a phenyl group, a halogen group, an alkoxy group, etc., as specified in the above formula (1). The substitution position is not limited and may be arbitrarily selected. Ar in the above chemical formula (1) is preferably a group having a benzene ring structure in place of three hydrogen atoms from the viewpoints of polymerizability, mechanical characteristics, and color tone.
R1 in the chemical 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. Preferably an alkyl group having 1 to 3 carbon atoms such as a hydrogen atom, methyl group, ethyl group, propyl group and the like. Among them, R1 in the above chemical formula (1) is preferably a methyl group or an ethyl group from the viewpoints of polymerizability, mechanical properties and color tone.
R2 in the chemical 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. Preferably an alkyl group having 1 to 3 carbon atoms such as a hydrogen atom, methyl group, ethyl group, propyl group and the like. Among them, R2 in the above chemical formula (1) is preferably a methyl group or an ethyl group from the viewpoints of polymerizability, mechanical properties and color tone.
R1 and R2 in the above chemical formula (1) may have the same structure or different structures. R1 and R2 in the chemical formula (1) are independent of each other, and may have any structure within the above range.
M in the above chemical formula (1)+Is a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion. Further, M in the above chemical formula (1)+In the case of polyvalent, a corresponding number of sulfonic acid groups (except M in the above chemical formula (1)) is provided+Other portions). For example, M in the above chemical formula (1)+In the case of a 2-valent metal ion, 2 sulfonic acid groups (except M in the above chemical formula (1)) are associated with 1 metal ion+Other portions).
Examples of the metal ions include alkali metal ions such as sodium ions, potassium ions, and lithium ions; alkaline earth metal ions such as calcium ions and magnesium ions; and zinc ions, etc. Examples of the tetraalkylphosphonium ion include tetrabutylphosphonium ion and tetramethylphosphonium ion. As tetraalkylammonium ions as described aboveExamples of the cation include tetrabutylammonium ion and tetramethylammonium ion. Wherein M in the above chemical formula (1)+From the viewpoints of polymerizability, mechanical properties, antistatic properties and color tone, alkali metal ions, tetrabutylammonium ions and tetrabutylphosphonium ions are preferable. More preferred are alkali metal ions and tetrabutylphosphonium ions.
Examples of the above-mentioned component (b2), i.e., the aromatic polycarboxylic acid having a sulfonate group substituted therein and/or the ester-forming derivative thereof represented by the above chemical formula (1), include sodium 4-sulfonate isophthalate, 5-sulfonate isophthalate, potassium 4-sulfonate isophthalate, potassium 5-sulfonate isophthalate, 2-sulfonate sodium terephthalate, potassium 2-sulfonate terephthalate, zinc 4-sulfonate isophthalate, 5-sulfonate isophthalic acid, 2-sulfonate sulfo-terephthalate, tetraalkylphosphonium isophthalate, 4-sulfonate tetraalkylphosphonium isophthalate, tetraalkylammonium isophthalate, and the like, 5-tetraalkylammonium isophthalate-sulfonate, 2-tetraalkylphosphonium terephthalate-sulfonate, 2-tetraalkylammonium terephthalate-sulfonate, 4-sodium 2, 6-naphthalenedicarboxylate, 4-sodium 2, 7-naphthalenedicarboxylate, potassium 2, 6-naphthalenedicarboxylate, zinc 2, 6-naphthalenedicarboxylate-4-sulfonate, tetraalkylphosphonium 2, 6-naphthalenedicarboxylate, tetraalkylphosphonium 2, 7-naphthalenedicarboxylate, dimethyl ester of these compounds, diethyl ester of these compounds, and the like.
Among these, as the component (b2), dimethyl isophthalate-4-sulfonate, dimethyl isophthalate-5-sulfonate, dimethyl isophthalate-4-sulfonate potassium, dimethyl isophthalate-5-sulfonate potassium, dimethyl terephthalate-2-sulfonate sodium and dimethyl terephthalate-2-sulfonate potassium are preferable in view of polymerizability, mechanical properties and color tone.
The component (B) contains 70 to 98 mol%, preferably 71 to 97 mol%, more preferably 73 to 95 mol%, and still more preferably 75 to 91 mol% of the structural unit derived from the component (B1) and 2 to 30 mol%, preferably 3 to 29 mol%, more preferably 5 to 27 mol%, and still more preferably 9 to 25 mol% of the structural unit derived from the component (B2), based on 100 mol% of 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).
When the component (B) includes the structural unit derived from the component (B1) and the structural unit derived from the component (B2) within the above range, the antistatic property of the antistatic resin composition of the present invention is more excellent. In addition, the antistatic property can be kept well even if washing and wiping are carried out. In addition, the resin composition has sufficient molecular weight and crystallinity, and is excellent in handling properties.
When the component (B) contains a structural unit derived from a polyalkylene glycol (B3) having a number average molecular weight of 200 to 50000, antistatic properties are more excellent, and therefore, it is preferable.
Examples of the polyalkylene glycol having a number average molecular weight of 200 to 50000 which is the component (b3) include polyethylene glycol, polypropylene glycol, a copolymer having ethylene glycol as a main monomer (usually 60 mol% or more, preferably 80 mol% or more) and propylene glycol as a comonomer, a copolymer having an alkylene glycol such as ethylene glycol or propylene glycol as a main monomer and a small amount (usually 10 mol% or less, preferably 5 mol% or less, more preferably 1 mol% or less) of an aromatic polyol as a comonomer, and a mixture thereof.
The number average molecular weight of the component (b3) may be 200 to 50000, preferably 500 to 30000, more preferably 1000 to 20000, from the viewpoint of antistatic properties, dispersibility and heat resistance.
The content of the structural unit derived from the component (B3) in the component (B) may be 10 to 60 mass%, preferably 15 to 55 mass%, more preferably 20 to 50 mass%, from the viewpoints of antistatic property, handling property and heat resistance. Wherein the sum of 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 content of the structural unit derived from the component (b4) is 100% by mass.
When the component (B) contains a structural unit derived from ethylene glycol (B4) having 2 to 10 carbon atoms, antistatic properties, handling properties, and heat resistance are further improved, and thus the component (B) is preferable.
Examples of the diol having 2 to 10 carbon atoms as the component (b4) include aliphatic diols such as ethylene glycol, propylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, 2-methyl-1, 3-propanediol, 1, 2-cyclohexanediol, and 1, 4-cyclohexanediol; ethylene glycol having an ether bond such as diethylene glycol; and glycols having a thioether bond such as thiodiethanol. As the component (b4), 1, 6-hexanediol, ethylene glycol and diethylene glycol are preferable from the viewpoints of antistatic property, crystallinity and handling property. As the component (b4), one or more of them can be used.
As the component (B), a component (a) according to JIS K7367-1: 2002, the reduced viscosity measured at a concentration of 1.2g/dl and a temperature of 35 ℃ using a mixed solvent of DIN Ubbelohde viscometer (capillary diameter 0.63mm) and phenol/tetrachloroethane (mass ratio 60/40) of FIG. 2 is preferably 0.2cm from the viewpoints of antistatic property, heat resistance and machine properties3More preferably 0.25 cm/g or more3A value of at least one gram, more preferably 0.3cm3At least one of the units is/g, and may be 1.8cm in view of antistatic property3The ratio of the carbon atoms to the carbon atoms is less than g.
The method for obtaining the component (B) from the components (B1) to (B4) is not particularly limited, and any method may be used. For example, the components (B1) to (B4) may be heated and melted to 150 to 300 ℃ in the presence of a transesterification catalyst to cause a polycondensation reaction to obtain the component (B).
The transesterification catalyst is not particularly limited, and any transesterification catalyst may be used. Examples of 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; calcium compounds such as calcium acetate; alkali metal salts such as sodium carbonate and potassium carbonate. Among them, tetrabutyl titanate is preferable. As the transesterification catalyst, one or more of them can be used.
The amount of the transesterification catalyst is not particularly limited, but may be usually 0.01 to 0.5 mol%, preferably 0.03 to 0.3 mol%, based on 1 mol of the component (b 1).
In addition, it is preferable to use various stabilizers such as an antioxidant together with the polycondensation reaction.
The polycondensation reaction is preferably carried out for about 1 to 20 hours at 150 to 250 ℃, preferably 150 to 200 ℃ while evaporating the distillate, and the temperature is raised to 180 to 300 ℃, preferably 200 to 280 ℃, more preferably 220 to 260 ℃, and then carried out for about 1 to 20 hours. The component (B) may be set to have a reduced viscosity in a preferred range.
Examples of the commercially available component (B) include "E L ECUTR02 (trade name)" available from Kagaku K.K.
The amount of the component (B) may be 7 parts by mass or more, preferably 9 parts by mass or more, and more preferably 12 parts by mass or more, per 100 parts by mass of the component (a), from the viewpoint of antistatic properties. On the other hand, it may be 25 parts by mass or less, preferably 22 parts by mass or less, more preferably 20 parts by mass or less, from the viewpoint of the emission gas resistance and the transparency.
(C) Ionic surfactant (optional ingredients):
the antistatic resin composition of the present invention, as described above, can find sufficient antistatic property even without using an ionic surfactant, but the use of an ionic surfactant is not excluded. In the case where the antistatic resin composition is used, for example, in an application where antistatic properties are particularly important in the initial stage, and an application where the necessity of problems of gas emission and bleeding is low is considered, the antistatic resin composition of the present invention may contain an ionic surfactant.
When the ionic surfactant as the component (C) is used, the amount to be blended is not particularly limited, and may be 0.5 to 5 parts by mass per 100 parts by mass of the component (a).
As the component (C), for example, an organic sulfonic acid type surfactant composed of an organic sulfonic acid and a base is exemplified.
Examples of the organic sulfonic acid 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 alkylnaphthalenesulfonic acids having 2 to 18 carbon atoms in the alkyl group such as dimethylnaphthalenesulfonic acid, diisopropylnaphthalenesulfonic acid, and dibutylnaphthalenesulfonic acid. Among them, dodecylbenzenesulfonic acid and dimethylnaphthalenesulfonic acid are preferable. As the organic sulfonic acid, one or more of them 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 ammonium compounds such as tetrabutylammonium, tributylbenzylammonium chloride, and triphenylbenzylammonium. Among them, sodium, potassium, tetramethylphosphonium, tetraethylphosphonium, tetrahexylphosphonium, tetraoctylphosphonium, tetrabutylphosphonium, tributylbenzylphosphonium, triethylhexadecylphosphonium and tetraphenylphosphonium are preferable. As the base, one or more of them can be used.
The component (C) is preferably a phosphonium compound from the viewpoint of the effect of suppressing the emission of gas and the antistatic property, and examples thereof include tetrabutylphosphonium dodecylbenzenesulfonate.
The volume resistivity of the antistatic resin composition of the present invention is preferably 1010Omega cm or less, more preferably 109～1010Omega cm. Further preferably, the volume resistivity is 109～1010Omega cm, the antistatic property can be maintained even if washing or wiping is performed.
In the present specification, the volume resistivity is a value measured according to the following experiment (2).
The amount of the gas emitted from the antistatic resin composition of the present invention is preferably 2. mu.g/g or less, more preferably 1. mu.g/g or less. In the case of ordinary use, the amount of the divergent gas is preferably 2. mu.g/g or less. Even in the use of precision electronic equipment and the like, which requires a low amount of emitted gas in particular, the amount of emitted gas can be favorably set to 1 μ g/g or less. In the present specification, the amount of the divergent gas is the amount (μ g) of the divergent gas generated from 1g of the sample measured according to the following experiment (5).
The antistatic resin composition of the present invention may contain, in addition to the above components, a thermoplastic resin other than the component (a) and the component (B) and a surfactant other than the component (C), a heat stabilizer, an antioxidant, a hydrolysis inhibitor, a metal deactivator, an ultraviolet absorber, an antistatic agent, a lubricant, a colorant, and the like, as required.
In the antistatic resin composition of the present invention, a heat stabilizer and an antioxidant are preferably contained. The molding problems such as coloring and burning can be prevented when a large molded article is molded. In the antistatic resin composition of the present invention, a metal deactivator is preferably contained. Even when used for a member in contact with a metal, corrosion and discoloration of the contact portion can be prevented.
Examples of the antioxidant include phenol antioxidants such as 2, 6-di-t-butyl-p-cresol, 2, 6-di-t-butylphenol, 2, 4-dimethyl-6-t-butylphenol, 4-dihydroxydiphenyl and tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, phosphite antioxidants, thioether antioxidants and the like. Among them, phenol-based antioxidants and phosphite-based antioxidants are preferable.
The antistatic resin composition of the present invention can be produced by melt-kneading the component (a), the component (B) and any component in any order or simultaneously. The method of melt kneading is not particularly limited, and a known method can be used. For example, a single-shaft extruder, a twin-shaft extruder, a roll, a stirrer, or various kneaders can be used. When a stirrer or a kneader is used, for example, it is preferable to melt-knead the mixture at a discharge temperature of 240 to 260 ℃. When a twin-screw kneader is used, it is preferable to perform melt kneading under conditions such that the number of revolutions of a paddle is 50 to 500rpm and the kneading temperature is 240 to 260 ℃.
The antistatic resin composition of the present invention can be molded into any molded article by a known molding method. Examples of the molding method include a general injection molding method, an insert molding method, a two-color molding method, a sandwich molding method, a gas injection method, a profile extrusion molding method, a two-color extrusion molding method, a cover molding method, and a sheet and film extrusion molding method.
Examples
The present invention will be described below with reference to examples, but the present invention is not limited thereto.
Measuring method
(1) Formability:
an injection molding machine with a mold closing force of 120 tons is used to mold an injection molding plate with a longitudinal length of 64.4mmm, a transverse length of 64.4mm and a thickness of 3mm under the conditions of a cylinder temperature of 240-260 ℃, a mold temperature of 50 ℃ and a cooling time of 5 minutes. The resulting plate was visually observed and evaluated according to the following criteria.
○ sink marks and warpage were not observed.
× confirmation of sink mark or warp, or confirmation of sink mark and warp
(2) Volume resistivity (antistatic property):
the measurement was performed by a double ring PROBE method (ring PROBE method) in accordance with astm d257 (1987 edition), in which the injection molded plate obtained by the method of the above experiment (1) was used as a test piece, and after the adjustment of the state at a temperature of 23 ± 2 ℃ and a relative humidity of 50 ± 5% for 40 hours or more in a laboratory, the measurement was performed using a resistivity meter "HIRESTA upmcpcb-HT 450 type (trade name)" of mitsubishi chemical corporation, a double ring PROBE (as a ring shape, having a main electrode outer diameter of 0.59cm and a guard electrode inner diameter of 1.1cm) "URS PROBE (trade name)" of mitsubishi chemical corporation, and a calculation platform "UF L (trade name)" of mitshi chemical corporation under the conditions of an applied voltage of 500V and a measurement time of 60 seconds, the measurement was performed at 2 measurement positions of 1 test piece, and 3 test pieces were measured, and the average value of the total 6 measurement values was used as the volume resistivity of the sample.
In addition, the resistivity measurement method and the theory thereof can be referred to a Web page (http:// www.mccat.co.jp/3 seihin/geni/ghlup 2.htm) of Mitsubishi chemical corporation, and the like.
(3) Volume resistivity after water washing (durability against static electricity 1):
the injection molded plate obtained by the method of the above experiment (1) was subjected to a method of measuring the volume resistivity according to the above experiment (2) by washing the surface of the plate with gauze (type 1 gauze for medical use, manufactured by Chuanyuan company, Ltd.) in a water tank filled with distilled water at 25 ℃ for 10 minutes, wiping off water with clean paper, and then drying the plate in a laboratory at a temperature of 23. + -. 2 ℃ and a relative humidity of 50. + -. 5% for 24 hours or more.
(4) Volume resistivity after wiping (durability against static electricity 2):
the injection molded plate obtained by the method of the above experiment (1) was placed on a friction tester of JIS L0849, a stainless steel plate (10 mm in the vertical direction, 10mm in the horizontal direction, and 1mm in thickness) covered with 4 pieces of gauze (medical type 1 gauze of chuanbei corporation) was attached to a friction terminal of the friction tester in a superposed manner, the long and wide surface of the stainless steel plate was placed in contact with the test piece, a load of 350g was applied, the test piece was wiped back and forth 300 times at a speed of 1 back and forth/sec at a moving distance of the friction terminal of 60mm, and then the volume resistivity of the wiped portion of the test piece was measured by the method of the above experiment (2).
(5) Amount of divergent gas:
the measurement can be performed using a thermal desorption gas chromatography mass spectrometer of perkin elmer.
(5-1) capturing the off-gas by thermal desorption:
the resin composition was frozen and pulverized into 2mm or less squares, 0.1g of the pulverized material obtained in the above manner was placed in a sample tray of the trap unit of the above apparatus, heated at 120 ℃ for 10 minutes, and the volatile substances generated were trapped in a cooling trap tube maintained at 5 ℃ using helium as a carrier gas.
(5-2) quantification of volatile substances (outgassing):
the cooled collection tube in which the volatile substance was collected in (5-1) was heated to 300 ℃ at a temperature rise rate of 40 ℃/sec, and the desorbed gas was supplied to a gas chromatography mass spectrometer unit of the apparatus to quantify the amount of the gas generated, in this case, a certain amount of n-decane was impregnated into a standard sample (TenaxTA (trade name) "made by G L sciences Co., Ltd., a weakly polar porous polymer bead adsorbent based on 2, 6-diphenyl-p-phenylene oxide), and a detection line was prepared by the same measurement as described above.
(6) Haze value (transparency):
an injection molding machine with a mold closing force of 120 tons is used to mold an injection molding piece with a longitudinal direction of 60mm, a transverse direction of 60mm and a thickness of 0.5mm under the conditions of a cylinder temperature of 240-260 ℃, a mold temperature of 50 ℃ and a cooling time of 5 minutes, and the injection molding piece is prepared according to JIS K7136: 2000, haze value of the molded piece obtained by measurement using a nephelometer "NDH 2000 (trade name)" manufactured by Nippon Denshoku industries Co., Ltd. The evaluation was performed on the following criteria.
◎ is less than 5%
○ is more than 5% and less than 50%
× percent more than 50 percent
(7) Heat distortion temperature (heat resistance):
a test piece having a length of 127mm, a height of 13mm and a thickness of 6mm was molded by an injection molding machine having a mold closing force of 120 tons at a cylinder temperature of 240 to 260 ℃, a mold temperature of 50 ℃ and a cooling time of 5 minutes according to ASTM D648-07, and the measurement was carried out using the test piece under conditions of a distance between fulcrums of 100.0mm (method B), a load of 1.82MPa and a temperature raising speed of 2 ℃.
Raw materials used
(A) Polyester-based resin:
(A-1) the polyester-based resin comprising 100 mol% of a structural unit derived from terephthalic acid, based on 100 mol% of the total of structural units derived from a polycarboxylic acid, and 77 mol% of a structural unit derived from 1, 4-cyclohexanedimethanol and 23 mol% of a structural unit derived from 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol, based on 100 mol% of the total of structural units derived from a polyol. The glass transition temperature is 108 ℃, and the heat of fusion is 0J/g (no obvious melting peak appears in a DSC second melting curve).
(A-2) the polyester-based resin comprising 100 mol% of a structural unit derived from terephthalic acid, based on 100 mol% of the total of structural units derived from a polycarboxylic acid, and comprising 64 mol% of a structural unit derived from 1, 4-cyclohexanedimethanol and 36 mol% of a structural unit derived from 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol, based on 100 mol% of the total of structural units derived from a polyol. The glass transition temperature is 119 ℃, and the heat of fusion is 0J/g (no obvious melting peak appears in a DSC second melting curve).
(A') comparative resin:
(A' -1) the polyester-based resin comprising 100 mol% of a structural unit derived from terephthalic acid, based on 100 mol% of the total of structural units derived from a polycarboxylic acid, and comprising 34 mol% of a structural unit derived from 1, 4-cyclohexanedimethanol and 66 mol% of a structural unit derived from ethylene glycol, based on 100 mol% of the total of structural units derived from a polyhydric alcohol. The glass transition temperature is 81 ℃, and the heat of fusion is 0J/g (no obvious melting peak appears in a DSC second melting curve).
(A' -2) polycarbonate resin manufactured by Mitsubishi engineering plastics corporation "IUPI L ON3000 (trade name)".
(B) Polyether ester resin:
(B-1) A polyether ester resin obtained in accordance with the procedure of paragraph 0063 of Japanese patent application laid-open No. 8-283548 and the contents of reference example 1. The component (b1) is dimethyl terephthalate, the component (b2) is dimethyl isophthalate-5-sodium sulfonate, 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 taken as 100 mol%, the structural unit derived from the component (b1) is set to 75 mol%, and the structural unit derived from the component (b2) is set to 25 mol%. The sum of 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 content of the structural unit derived from the component (b4) was defined as 100 mass%, and the content of the structural unit derived from the component (b3) was 11 mass%.
(B-2) a polyether ester resin obtained in accordance with the procedure of paragraph 0064 of Japanese patent application laid-open No. 8-283548 and the contents of reference example 2. The component (b1) is dimethyl terephthalate, the component (b2) is dimethyl isophthalate-5-sodium sulfonate, 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) was defined as 100 mol%, the structural unit derived from the component (b1) was set to 85 mol%, and the structural unit derived from the component (b2) was set to 15 mol%. The sum of 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 content of the structural unit derived from the component (b4) was defined as 100 mass%, and the content of the structural unit derived from the component (b3) was 20 mass%.
(B-3) A polyether ester resin obtained in accordance with the procedure of paragraph 0065 of Japanese patent application laid-open No. 8-283548 and the contents of reference example 3. The component (b1) is dimethyl terephthalate, the component (b2) is dimethyl isophthalate-5-sodium sulfonate, 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) was defined as 100 mol%, the structural unit derived from the component (b1) was set to 75 mol%, and the structural unit derived from the component (b2) was set to 25 mol%. The sum of 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 content of the structural unit derived from the component (b4) was defined as 100 mass%, and the content of the structural unit derived from the component (b3) was 20 mass%.
(B-4) A polyether ester resin obtained in accordance with the procedure of paragraph 0066 of Japanese patent application laid-open No. 8-283548 and the contents of reference example 4. The component (b1) was dimethyl terephthalate, the component (b2) was dimethyl isophthalate-5-sodium sulfonate, the component (b3) was polyethylene glycol (number average molecular weight 4000), and the component (b4) was 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) was defined as 100 mol%, the structural unit derived from the component (b1) was set to 75 mol%, and the structural unit derived from the component (b2) was set to 25 mol%. The sum of 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 content of the structural unit derived from the component (b4) was defined as 100 mass%, and the content of the structural unit derived from the component (b3) was 20 mass%.
(B') comparative polyetherester resin:
(B' -1) Polyetheresteramide resin "PE L ESTAT 6321NC (trade name)" available from Sanyo chemical Co., Ltd.
(C) Ionic surfactants
(C-1) Kanto chemical Co., LtdSodium dodecylbenzenesulfonate.
Examples 1 to 11 and examples 1C to 7C
Use of
The co-rotating twin-screw kneader of (1) to (3) is a kneader in which a compound having a compounding ratio shown in any one of tables 1 to 3 is melt-kneaded at a set temperature of 240 to 260 ℃ to obtain a resin composition. The above experiments (1) to (7) were carried out. The results are shown in tables 1 to 3.
TABLE 1
TABLE 2
TABLE 3
The resin composition of the present invention is excellent in moldability, antistatic properties, antistatic durability, low gas emission properties, transparency and heat resistance.
Claims (8)
1. An antistatic resin composition, comprising:
100 parts by mass of a polyester-based resin (A) having the following characteristics (a1) and (a 2); and
7 to 25 parts by mass of a polyether ester resin (B) having a structural unit derived from an aromatic polycarboxylic acid substituted with a sulfonate group,
(a1) the total of the structural units derived from the polycarboxylic acid is defined as 100 mol%, and the total of the structural units derived from the polycarboxylic acid is defined to contain 90 to 100 mol% of the structural unit derived from terephthalic acid and 0 to 10 mol% of the structural unit derived from isophthalic acid,
(a2) the total of the structural units derived from the polyol is defined as 100 mol%, and the structural units derived from 1, 4-cyclohexanedimethanol comprise 50 to 90 mol% and 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol comprise 10 to 50 mol%.
2. The antistatic resin composition according to claim 1,
the component (B) is a polyetherester resin comprising:
a structural unit derived from at least one aromatic dicarboxylic acid (b1) 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;
a structural unit derived from an aromatic polycarboxylic acid substituted with a sulfonate group and/or an ester-forming derivative thereof (b2) represented by the following chemical formula (1);
a structural unit derived from a polyalkylene glycol (b3) having a number average molecular weight of 200 to 50000; and
a structural unit derived from a C2-10 diol (b4),
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 defined as 100 mol%, and the sum includes 70 to 98 mol% of the structural unit derived from the component (b1) and 2 to 30 mol% of the structural unit derived from the component (b2),
the sum of 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 content of the structural unit derived from the component (b4) was defined as 100% by mass,
the content of the structural unit derived from the component (b3) is 10 to 60 mass%,
chemical formula 1
In the chemical formula 1, the first and second,
ar represents a group having an aromatic ring structure substituted for at least three hydrogen atoms;
r1 and R2 each independently represent 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 tetraalkyl phosphonium ion or a tetraalkyl ammonium ion.
3. The antistatic resin composition according to claim 1 or 2,
the composition further contains 0.5 to 5 parts by mass of an ionic surfactant (C) per 100 parts by mass of the component (A).
4. The antistatic resin composition according to claim 1 or 2,
volume resistivity is 109～1010Ω·cm。
5. The antistatic resin composition according to claim 1 or 2,
further contains 0.5 to 5 parts by mass of an ionic surfactant (C) per 100 parts by mass of the component (A), and has a volume resistivity of 109～1010Ω·cm。
6. The antistatic resin composition according to claim 1 or 2,
an antistatic resin composition is used, an injection molding piece with the thickness of 0.5mm is molded by using an injection molding machine with the mold closing force of 120 tons under the conditions of the cylinder temperature of 240-260 ℃, the mold temperature of 50 ℃ and the cooling time of 5 minutes, and the obtained molding piece is prepared according to the following steps of JIS K7136: the haze value measured by 2000 is 5% or more and less than 50%.
7. A molded article comprising the antistatic resin composition according to any one of claims 1 to 6.
8. A precision electronic device comprising the antistatic resin composition according to any one of claims 1 to 6.
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| PCT/JP2016/072211 WO2017022637A1 (en) | 2015-08-05 | 2016-07-28 | Antistatic resin composition |
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| KR20230071116A (en) * | 2020-09-24 | 2023-05-23 | 리껭테크노스 가부시키가이샤 | Antistatic resin composition, resin film, and base film for antistatic dicing tape |
| 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 |
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| CN1882649A (en) * | 2003-11-26 | 2006-12-20 | 伊斯曼化学公司 | Polyester compositions for calendering |
| JP2009001618A (en) * | 2007-06-19 | 2009-01-08 | Riken Technos Corp | Antistatic polyester resin composition |
| CN101555636A (en) * | 2008-04-09 | 2009-10-14 | 东丽纤维研究所（中国）有限公司 | Antistatic polyester fiber |
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| JPS62230835A (en) | 1986-03-31 | 1987-10-09 | Takemoto Oil & Fat Co Ltd | Antistatic agent for synthetic polymer |
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- 2016-07-28 WO PCT/JP2016/072211 patent/WO2017022637A1/en active Application Filing
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- 2016-07-28 CN CN201680044661.1A patent/CN107849340B/en active Active
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| CN1882649A (en) * | 2003-11-26 | 2006-12-20 | 伊斯曼化学公司 | Polyester compositions for calendering |
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| Publication number | Publication date |
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| JPWO2017022637A1 (en) | 2018-06-07 |
| KR20180037214A (en) | 2018-04-11 |
| KR102513777B1 (en) | 2023-03-24 |
| TW201718760A (en) | 2017-06-01 |
| WO2017022637A1 (en) | 2017-02-09 |
| JP6656253B2 (en) | 2020-03-04 |
| CN107849340A (en) | 2018-03-27 |
| TWI715604B (en) | 2021-01-11 |
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