WO2017022637A1

WO2017022637A1 - Antistatic resin composition

Info

Publication number: WO2017022637A1
Application number: PCT/JP2016/072211
Authority: WO
Inventors: さゆり猪俣; 和香子小林
Original assignee: リケンテクノス株式会社
Priority date: 2015-08-05
Filing date: 2016-07-28
Publication date: 2017-02-09
Also published as: TW201718760A; JPWO2017022637A1; CN107849340A; TWI715604B; KR20180037214A; CN107849340B; KR102513777B1; JP6656253B2

Abstract

[Problem] To provide an antistatic resin composition which has excellent transparency, heat resistance and antistatic properties, especially excellent sustainability of antistatic properties, while being free from problems of outgas. [Solution] An antistatic resin composition which contains 100 parts by mass of (A) a polyester resin having the characteristics (a1) and (a2) described below and 7-25 parts by mass of (B) a polyether ester resin having a structural unit derived from an aromatic polyvalent carboxylic acid substituted by a sulfonate group. (a1) When the sum of the structural units derived from polyvalent carboxylic acids is taken as 100% by mole, 90-100% by mole of a structural unit derived from terephthalic acid and 10-0% by mole of a structural unit derived from isophthalic acid are contained. (a2) When the sum of the structural units derived from polyhydric alcohols is taken as 100% by mole, 50-90% by mole of a structural unit derived from 1, 4-cyclohexane dimethanol and 50-10% by mole of a structural unit derived from 2, 2, 4, 4-tetramethyl-1, 3-cyclobutane diol are contained.

Description

Antistatic resin composition

The present invention relates to an antistatic resin composition. More specifically, the present invention relates to a polyester resin composition having antistatic properties.

Since precision electronic components such as semiconductor wafers, semiconductor elements, and integrated circuits may be damaged by a slight charge (so-called electrostatic breakdown), their transport trays, packaging materials, and storage The material used for the tool and the exterior member is required to have a volume resistance value of 10 9 to 10 10 Ω · cm. In addition, 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. Preferably, 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. Furthermore, 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 ℃.

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 Ω · cm have been proposed and put into practical use.

As the above technology, for example, 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. (For example, Patent Documents 1 and 2). However, since these technologies lower the electrical resistance value by causing a low molecular weight surfactant to ooze out on the surface of the molded article, the surface surfactant is wiped off or washed. As a result, there is a problem that the antistatic property is lowered (an electric resistance value is increased) and that outgas is generated.

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. However, in these techniques, it is necessary to blend a large amount of thermoplastic resin having antistatic properties in order to obtain sufficient antistatic properties. Moreover, the heat resistance and transparency are not satisfactory. In addition, 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.

Further, as the above-mentioned antistatic thermoplastic resin, 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.) By polycondensing a polyether ester obtained by condensing (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. 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.

Therefore, it has been proposed to use an ionic surfactant in combination (for example, paragraph 0031 of Patent Document 7 and Patent Document 11). However, in these techniques, reduction of antistatic property due to washing and wiping, generation of outgas, and the like. There is a problem.

Therefore, in 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.

Japanese Patent Laid-Open No. 5-222241 JP-A-62-230835 JP-A-62-273252 JP-A-5-97984 Japanese Patent Laid-Open No. 3-255161 JP-A-5-222289 JP-A-6-57153 JP-A-8-283548 Japanese Patent Laid-Open No. 10-219095 JP 2006-022232 A JP-A-8-283548 JP 2009-001618 A

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 Ω · 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.

As a result of intensive studies, the present inventor has found that the above-described problems can be achieved by a resin composition of a specific polyester resin and a specific polyether ester.

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.

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.

In formula (1),
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.

According to a third aspect of the present invention, 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.

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 Ω · 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 Ω · 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.

This is a measurement example of ¹ H-NMR of a polyester resin.

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.

(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.

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. Examples of 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 acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid; and ester-forming derivatives thereof. One or more of these may be used as the other polycarboxylic acid.

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, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bisphenol A, alkylene oxide adducts of bisphenol A; and ester-forming derivatives thereof Etc. One or more of these can be used as the polyvalent ol.

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. Become. In addition, 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.

In this specification, a Diamond DSC type differential scanning calorimeter manufactured by PerkinElmer Japan Co., Ltd. is used, and the sample is held at 320 ° C. for 5 minutes, then cooled to −50 ° C. at a temperature decrease rate of 20 ° C./min, and −50 The second melting curve (melting curve measured in the last heating step) measured by a temperature program of holding at 5 ° C. for 5 minutes and then heating to 320 ° C. at a heating rate of 20 ° C./min, A polyester resin of 10 J / g or less was defined as non-crystalline, and a polyester resin of more than 10 J / g and 60 J / g or less was defined as low crystallinity.

In this specification, 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 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)

^{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)

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.

(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.

In the formula (1), 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. 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. Among these, as 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.

In the above formula (1), 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. In addition, when 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. For example, when 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. Examples of the tetraalkylphosphonium ion include tetrabutylphosphonium ion and tetramethylphosphonium ion. Examples of the tetraalkylammonium ion include tetrabutylammonium ion and tetramethylammonium ion. Among these, as M ⁺ in the above formula (1), 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. 5-sodium sulfo-isophthalic acid, 4-potassium sulfo-isophthalic acid, 5-potassium sulfo-isophthalic acid, 2-sodium sulfo-terephthalic acid, 2-potassium sulfo-terephthalic acid, zinc 4-sulfo-isophthalic acid, 5 -Zinc sulfo-isophthalate, zinc 2-sulfo-terephthalate, 4-sulfo-isophthalic acid tetraalkylphosphonium salt, 5-sulfo-isophthalic acid tetraalkylphosphonium salt, 4-sulfo-isophthalic acid tetraalkylammonium salt, 5- Sulfo-isophthalic acid tetraalkylammonium salt, 2- Rufo-terephthalic acid tetraalkylphosphonium salt, 2-sulfo-terephthalic acid tetraalkylammonium salt, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid, 4-sodium sulfo-2,7-naphthalenedicarboxylic acid, 4-potassium sulfone -2,6-naphthalenedicarboxylic acid, 4-sulfo-2,6-naphthalenedicarboxylic acid zinc salt, 4-sulfo-2,6-naphthalenedicarboxylic acid tetraalkylphosphonium salt, 4-sulfo-2,7-naphthalenedicarboxylic acid Examples thereof include tetraalkylphosphonium salts, dimethyl esters thereof, and diethyl esters thereof.

Among them, 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. , 5-potassium 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%.

When the component (B) includes the structural unit derived from the component (b1) and the structural unit derived from the component (b2) so as to fall within the above range, 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.

It is preferable that 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. Here, 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.

It is preferable that 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 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 viewpoint of antistatic properties, crystallinity, and handleability. One or more of these can be used as the component (b4).

In accordance with JIS K7367-1: 2002 of the above component (B), a DIN Ubbelohde viscometer (capillary diameter 0.63 mm) and a mixed solvent of phenol / tetrachloroethane (mass ratio 60/40) shown in FIG. 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. ³ / g or more, more preferably 0.3 cm ³ / g or more, and from the viewpoint of antistatic properties, it may be 1.8 cm ³ / g or less.

The method for obtaining the component (B) using the components (b1) to (b4) is not particularly limited, and can be performed by any method. For example, 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. 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. 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).

In addition, it is preferable to use various stabilizers such as an antioxidant in the polycondensation reaction.

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.

As a commercial example of the above component (B), “Elecut R02 (trade name)” by Takemoto Yushi Co., Ltd. can be exemplified.

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). . On the other hand, from the viewpoint of outgas resistance and transparency, it is 25 parts by mass or less, preferably 22 parts by mass or less, more preferably 20 parts by mass or less.

(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.

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). .

Examples of the component (C) include an organic sulfonic acid type surfactant composed of an organic sulfonic acid and a base.

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 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. Of these, 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 volume resistivity of the antistatic resin composition of the present invention is preferably 10 10 Ω · cm or less, more preferably 10 9 to 10 10 Ω · cm. More preferably, the volume resistivity is 10 9 to 10 10 Ω · cm, and the antistatic property is maintained even after washing with water or wiping.

In this specification, 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 μg / g or less, more preferably 1 μg / g or less. If it is a normal use, it can be preferably used when the outgas amount is 2 μg / 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 μg / g or less. In this specification, the amount of outgas is the amount (μg) of outgas generated from 1 g of the sample, measured according to the following test (5).

In addition to the above components, 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.

It is preferable that 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.

Examples of the antioxidant 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. For example, a single screw extruder, a twin screw extruder, a roll, a mixer, or various kneaders can be used. When using a mixer or kneader, for example, it is preferable to perform melt-kneading under conditions of a discharge temperature of 240 to 260 ° C. When a biaxial kneader is used, it is preferable to perform 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. Examples of 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 For example, a film extrusion method can be used.

Hereinafter, although an example explains the present invention, the present invention is not limited to these.

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

(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.

(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).

(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).

(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.

(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%

(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.

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 ′) 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) 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 ′) 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) Ionic surfactant (C-1) Sodium dodecylbenzenesulfonate from Kanto Chemical Co., Inc.

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.

The resin composition of the present invention is excellent in moldability, antistatic properties, antistatic durability, low outgas properties, transparency, and heat resistance.

Claims

(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.
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.

In formula (1),
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 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).
4. The antistatic resin composition according to claim 1, having a volume resistivity of 10 9 to 10 10 Ω · cm.
An article comprising the antistatic resin composition according to any one of claims 1 to 4.
A precision electronic device comprising the antistatic resin composition according to any one of claims 1 to 4.