JP2000309691A - Antistatic pbt-based resin composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antistatic PBT-based resin composition capable of exhibiting antistatic effect permanently, having little deposition of colored degenerated resin near the outlet of an extruder during molding and useful as an electronic material or the like by formulating a PBT-based resin, a specific polyether ester and the like at specific ratios. SOLUTION: This resin is formulated with (A) 100 pts.wt. of a PBT-based resin, (B) 5-30 pts.wt. of a polyether ester obtained by the polycondensation of (i) a 6-20C dicarboxylic acid and/or its ester, (ii) a poly(alkylene oxide)glycol having a number average molecular weight of 200-50,000 and (iii) a 2-10C glycol, and (C) 0.5-6 pts.wt. of a surfactant. A compound of the formula (Ar is a 6-12C trivalent aromatic group; R1 and R2 are each H or the like; M+ is a metal ion or the like) in an amount of 3-50 mol.% is formulated in the component (i). The compounding ratio of the component (ii) in the component B is 40-90 wt.%. The reduced viscosity (conc. of 1.2 g/dl) of the component B determined in a mixed solvent of phenol/tetrachloroethane (60/40 by weight) at 35 deg.C is 1.0-5.0.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a PBT resin composition having an antistatic effect. More specifically, PB
The present invention relates to a PBT-based resin composition that does not generate foreign matter during melt-kneading and molding of a T resin and a polyetherester and has a long antistatic effect, and a method for producing the same.

[0002]

2. Description of the Related Art Plastic materials have been used as electric and electronic members, automobile members, medical members, household goods, and various other molded articles by utilizing their excellent characteristics. By the way, plastics generally have the property of high electrical insulation, but because of this, the static electricity that is charged is unlikely to dissipate, causing dust to adhere to products, electric shock to workers,
Problems such as malfunctions of instruments and IC chips have occurred. Therefore, research on antistatic methods for various plastic materials has been conducted.

[0003] As a method for preventing static charge of plastics, there are an internal addition type and a coating type. The coating type requires a separate step, and the internal addition type is more advantageous in the manufacturing process.

In the internal addition type method, a method of kneading a ionic surfactant such as an alkyl sulfonate or an alkylbenzene sulfonate into a polymer has been generally adopted because of its excellent effect and economy. Was. Among them, many of them using an alkyl (aryl) sulfonate have been practiced. Under these circumstances, examples of those having an antistatic effect are disclosed in, for example, JP-A-7-18.
No. 137 discloses a composition comprising a methyl methacrylate-styrene copolymer resin and a phosphonium sulfonate. This is because the surfactant seeps out to the surface, it shows an excellent antistatic effect with the addition of a small amount of phosphonium sulfonate, but it can be wiped,
There is a problem that the antistatic effect is reduced by washing with water.

On the other hand, as a method for imparting a permanent antistatic effect, a method of mixing an antistatic polymer has been disclosed. For example, JP-A-58-11838 discloses that a composition comprising a polyolefin and a polyetheresteramide has an antistatic effect. However, when such polymers are mixed with each other, when an injection molding machine or an extrusion molding machine is used to obtain a final molded product, a colored deteriorated foreign substance called "eye-and-eye" is generated in a path of the molten polymer, and the product is contained in the product. There is a problem that it is mixed and causes a defective molded product.

[0006] Japanese Patent Application Laid-Open No. 6-57153 reports a polyetherester comprising a polyalkylene glycol, a glycol and a polycarboxylic acid. Although this has permanent antistatic properties, its effect is insufficient when used alone. To further improve the effect, it is necessary to use an ionic antistatic agent in combination. However, in such a case, there is a problem that the antistatic effect is considerably reduced by washing with water. In JP-A-8-337702, in order to solve these problems, an acrylic resin is used in combination with a polyetherester obtained by copolymerizing an aromatic dicarboxylic acid component whose nucleus is substituted with a sulfonate group and a surfactant. By mixing, a permanent antistatic effect is exhibited. However, polycondensation-based thermoplastic resins such as the above-mentioned acrylic resins and other vinyl-based thermoplastic resins and PBT resins must be used together with polyalkylene glycol in order to provide better antistatic properties. It is necessary to increase the amount of polymerization, but when the amount of the component is large, the degree of polymerization is not easily increased by the method described in JP-A-8-337702, and when the degree of polymerization is low, the same as the above polyetheresteramide is used. There is a problem that a problem such as "eyes" occurs. In addition, problems such as deterioration with respect to light have occurred.

As described above, it has been difficult to obtain a PBT resin composition having a permanent antistatic effect, good physical properties, light resistance, and heat resistance. Especially when the copolymerization amount of poly (alkylene oxide) glycol is large,
It has been difficult to reach a degree of polymerization that does not cause "eye flaws" or the like, even if a long polymerization time is applied to a conventionally known polymerization method.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a permanent antistatic effect, and to reduce the generation of "eyes" during molding, and to reduce the deterioration of physical properties, moldability, light resistance and heat resistance.
An object of the present invention is to provide a BT resin composition. Furthermore, since the antistatic resin composition can be manufactured at low cost using conventional polyester manufacturing equipment, its industrial significance is significant.

[0009]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a specific polyether containing a specific aromatic dicarboxylic acid component whose nucleus is substituted by a sulfonate group. A new method for increasing the degree of polymerization of esters has been found, and the polyetherester and surfactant
It has been found that, by mixing with a T-based resin, a PBT-based resin composition which exhibits a permanent antistatic effect and further has a small decrease in physical properties, moldability, light resistance and heat resistance can be obtained. Reached.

That is, the present invention relates to a PBT resin (A) 1
00 parts by weight, dicarboxylic acid having 6 to 20 carbon atoms and / or its ester (B1), (B2) number average molecular weight 200
Poly (alkylene oxide) glycol (B2) having a molecular weight of up to 50,000 and polyether ester (B) obtained by polycondensing glycol (B3) having 2 to 10 carbon atoms.
In a resin composition comprising 0 part and 0.5 to 6 parts by weight of a surfactant (C), the above (B1) is represented by the following formula (1)

[0011]

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[In the formula (1), Ar represents 3 to 6 carbon atoms.
A valent aromatic group, R ¹ and R ² each independently represent a hydrogen atom,
Represents 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 tetraalkylphosphonium ion or a tetraalkylammonium ion. ] The aromatic dicarboxylic acid and / or its ester (B1 ') substituted with a sulfonic acid group represented by the formula (1) is contained in an amount of 3 to 50 mol% of the total acid component (B1), and constitutes the polyetherester (B). The content of (B2) is 40 to 9 of the total amount of (B1), (B2) and (B3).
0% by weight and the polyetherester (B) is phenol / tetrachloroethane (weight ratio of 6).
(0/40) in a mixed solvent at 35 ° C. of a reduced viscosity (concentration: 1.2 g / dl) of 1.0 to 5.0, which is an antistatic PBT resin composition.

Hereinafter, the present invention will be described in detail. The resin composition of the present invention substantially comprises a PBT resin (A), a polyetherester (B), and a surfactant (C).

In the present invention, the polyetherester (B) is phenol / tetrachloroethane (weight ratio of 6).
0/40) in a mixed solvent at 35 ° C. (concentration 1.2 g / dl) of 1.0 or more and 5.0 or less. If the reduced viscosity is smaller than 1.0, heat resistance and mechanical properties may be reduced. In addition, when using an injection molding machine or an extrusion molding machine to obtain the final molded product, a colored deteriorated foreign substance called "eye-to-eye" is generated in the path of the molten polymer, and is mixed into the product to remove the defective molded product. Cause. The upper limit for the reduced viscosity is, if the polymer is a substantially linear polymer,
Although a higher one is preferable in terms of both the antistatic effect and the mechanical properties, the practical upper limit of the polymerization is about 5.0. The reduced viscosity is more preferably 2.0 or more and 5.0 or less, and still more preferably 3.0 or more and 5.0 or less.

The acid component constituting the polyetherester (B) in the present invention is a sulfonate group (-
SO3 ^- M ⁺⁾ is a substituted aromatic dicarboxylic acids and / or esters thereof (B1 ') aromatic dicarboxylic acids and / or esters thereof having 6 to 20 carbon atoms containing (B1) at.

Here, as the aromatic dicarboxylic acid (B1) having 6 to 20 carbon atoms, terephthalic acid, isophthalic acid,
Aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid can be mentioned. Examples of the aromatic dicarboxylic acid ester having 6 to 20 carbon atoms include dimethyl terephthalate, diethyl terephthalate, dimethyl isophthalate, diethyl isophthalate,
Examples thereof include dimethyl 2,6-naphthalenedicarboxylate, diethyl 2,6-naphthalenedicarboxylate, dimethyl 2,7-naphthalenedicarboxylate, and diethyl 2,7-naphthalenedicarboxylate. These may have a substituent such as an alkyl group or a halogen on the aromatic ring. Of these, terephthalic acid, 2,6-naphthalenedicarboxylic acid, dimethyl terephthalate, and dimethyl 2,6-naphthalenedicarboxylate are preferred from the viewpoint of handling properties.

The aromatic dicarboxylic acid and / or its ester (B1 ') substituted with a sulfonic acid salt group (-SO3 ^- M ⁺ ) used in the present invention is represented by the following formula (1)

[0018]

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## EQU1 ##

In the above formula (1), R ¹ and R ² 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, preferably a hydrogen atom or methyl And an alkyl group having 1 to 3 carbon atoms such as an ethyl group.

In the above formula (1), M ⁺ represents an ion selected from a metal ion, a tetraalkylphosphonium ion and a tetraalkylammonium ion. Examples of M ⁺ include alkali metal ions such as sodium ion, potassium ion and lithium ion, alkaline earth metal ions such as calcium ion and magnesium ion, metal ions such as zinc ion, tetrabutylphosphonium ion, tetramethylphosphonium ion and tetrabutyl. Ammonium ion or tetramethylammonium ion. Among these ions, metal ions are preferable, and alkali metal ions and zinc ions are more preferable. However, in the case of a divalent metal ion, one mole of the metal ion corresponds to 2 moles of the sulfonate group.

Ar in the above formula (1) is a trivalent aromatic group having 6 to 12 carbon atoms such as a benzene ring and a naphthalene ring, and these are also an alkyl group, a phenyl group, a halogen, or an alkoxy group. It may have a substituent such as a group.

The aromatic dicarboxylic acid includes 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, 4-sulfo- Zinc isophthalate, 5-sulfo-
Zinc isophthalate, zinc 2-sulfo-terephthalate, 4
Tetraalkylphosphonium sulfo-isophthalate, tetraalkylphosphonium 5-sulfo-isophthalate, tetraalkylammonium 4-sulfo-isophthalate, tetraalkylammonium 5-sulfo-isophthalate, tetra-sulfo-terephthalate Alkyl phosphonium salt, tetraalkyl ammonium 2-sulfo-terephthalate, 4-sodium sulfo-2,
6-naphthalenedicarboxylic acid, 4-sodium sulfo-
Examples thereof include 2,7-naphthalenedicarboxylic acid, 4-potassium sulfo-2,6-naphthalenedicarboxylic acid, and zinc salt of 4-sulfo-2,6-naphthalenedicarboxylic acid.

Examples of the aromatic dicarboxylic acid esters include dimethyl esters and diethyl esters of the aromatic dicarboxylic acids specifically listed above.

Among them, R ¹ and R ² are both methyl groups or both ethyl groups, Ar is a benzene ring,
M ⁺ is more preferably an alkali metal ion such as sodium or potassium in terms of polymerizability, mechanical properties, color tone, and the like.

More preferably, the aromatic dicarboxylic acid ester is dimethyl 4-sodium sulfo-isophthalate, dimethyl 5-sodium sulfo-isophthalate,
Dimethyl-potassium sulfo-isophthalate, dimethyl 5-potassium sulfoisophthalate, dimethyl 2-sodium sulfo-terephthalate, dimethyl 2-potassium sulfo-terephthalate, and the like.

According to the present invention, from the viewpoint of the antistatic effect,
Aromatic dicarboxylic acid and / or ester thereof (B1 ′) substituted with a sulfonic acid group represented by the above formula (1)
Is such that the compound represented by the formula (1) accounts for 3 to 50 mol% of the total acid component (B1) used, that is, 3 to 50 mol% of the acid component constituting the polyetherester. . When the content of the aromatic dicarboxylic acid and / or its ester (B1 ′) is less than 3 mol%, the antistatic effect is not sufficient. If it exceeds 50 mol%, the polymerization reaction becomes difficult, and it becomes difficult to obtain a polyetherester (B) having a sufficient degree of polymerization, and the handleability deteriorates. The aromatic dicarboxylic acid represented by the above formula (1) and / or
Alternatively, the ester thereof preferably accounts for 4 to 40 mol% of the total acid component, and more preferably accounts for 5 to 30 mol%.

The glycol component constituting the polyetherester (B) in the present invention has a number average molecular weight of 20.
It comprises a poly (alkylene oxide) glycol (B2) having 0 to 50,000 and a glycol (B3) having 2 to 6 carbon atoms.

Here, the poly (alkylene oxide) glycol (B2) includes polyethylene glycol, poly (propylene oxide) glycol, ethylene oxide adducts to bisphenols, poly (propylene oxide) glycol copolymerized polyethylene glycol, and the like. it can. Among them, poly (alkylene oxide) mainly composed of polyethylene glycol
Glycols are preferred. The poly (alkylene oxide) glycol (B2) has a number average molecular weight of 200 to 50.
000 is used. If the molecular weight is less than 200, a sufficient antistatic effect cannot be obtained. Also,
From the viewpoint of practicality, the upper limit of the molecular weight is about 50,000. The preferred number average molecular weight of the poly (alkylene oxide) glycol is from 500 to 40,000, more preferably from 1,000 to 30,000.

The poly (alkylene oxide) glycol (B2) must account for 40 to 90% by weight of the polyetherester in view of the antistatic effect. That is, the amount of the poly (alkylene oxide) glycol used is such that the content of (B2) constituting the polyetherester (B) is (B1), (B2) and (B2).
The content is set to 40 to 90% by weight based on the total amount of the preparation in 3). If the amount is less than 40% by weight, the antistatic effect is not sufficient, and if it is more than 90% by weight, the handleability and heat resistance tend to be poor. A preferred amount is 50% of the total polyetherester (B) obtained.
To 80% by weight, more preferably 55 to 75% by weight.
It is.

The poly (alkylene oxide) glycol (B2) is copolymerized with the polyetherester (B)
Has the greatest effect on the degree of polymerization obtained.

The glycol having 2 to 10 carbon atoms (B3) used in the present invention is specifically ethylene glycol, 1,4
-Butanediol, propylene glycol, 1,6-hexanediol (1,6-hexamethylene glycol), 3-methyl-1,5-pentanediol, and the like. These may contain an ether bond and a thioether bond. Among them, ethylene glycol, 1,6
-Hexanediol and 3-methyl-1,5-pentanediol are preferred in view of the antistatic effect.

The polyetherester (B) in the present invention contains the above component (B1 '), (B1), (B1)
2) and (B3) in the presence of a transesterification catalyst for 15
It can be obtained by heating and melting at 0 to 300 ° C. to cause a polycondensation reaction.

The transesterification catalyst is not particularly limited as long as it can be used for ordinary transesterification. Examples of such transesterification catalysts include antimony compounds such as antimony trioxide, stannous acetate, tin compounds such as dibutyltin oxide and dibutyltin diacetate, titanium compounds such as tetrabutyl titanate, zinc compounds such as zinc acetate, and calcium acetate. And alkali metal salts such as sodium carbonate and potassium carbonate. Of these, tetrabutyl titanate is preferably used.

The amount of the catalyst used may be the amount used in a usual transesterification reaction, and is generally preferably 0.01 to 0.5 mol% with respect to 1 mol of the acid component used.
0.03-0.3 mol% is more preferable.

In the reaction, it is also preferable to use various stabilizers such as an antioxidant described later.

(B1) including the above (B1 '), (B1)
As the temperature at which the compounds of 2) and (B3) are heated and melted and subjected to polycondensation, the esterification reaction and / or the transesterification reaction are carried out at 150 ° C. to 200 ° C. for several tens to ten and several hours as an initial reaction , And a polymerization reaction for increasing the molecular weight of the reaction product is performed at 180 ° C to 300 ° C.
If the temperature is lower than 180 ° C., the reaction does not proceed, and if the temperature is higher than 300 ° C., side reactions such as decomposition tend to occur. The polymerization reaction temperature is more preferably from 200 ° C to 280 ° C, even more preferably from 220 ° C to 250 ° C. The reaction time of this polymerization reaction depends on the reaction temperature and the amount of catalyst, but is usually about several tens to several tens of hours.

However, when only the above method is used, especially when the copolymerization amount of poly (alkylene oxide) glycol (B2) is large, the polymerization degree (phenol / tetrachloroethane (weight ratio 60/40)) falling within the range of the present invention is considered. Reduced viscosity measured at 35 ° C in a mixed solvent (concentration: 1.2 g / dl)
, 1.0 to 5.0) was difficult even if the polymerization time was extended.

By diligently studying this problem, we have found a method of obtaining poly (alkylene oxide) glycol (B2) in a short time despite the large amount of copolymerization.

That is, at the time of the above polymerization, the aromatic dicarboxylic acid and / or its ester (B1) is 0.5 to 1%.
By adding 0 mol% of the active ester compound,
It reacts effectively with the OH group at the terminal of the polymer present in the polymerization system in a short time to obtain the polyetherester (B) in the present invention. Examples of the active ester compound include an aromatic ester derivative and / or an aromatic carbonate, and more preferably, diphenyl carbonate and / or diphenyl terephthalate can be used. Furthermore, among diphenyl carbonate and diphenyl terephthalate, it is better to add diphenyl carbonate,
It is more preferable in terms of a small molecular weight and handling properties.

The amount of the active ester compound to be added is preferably 0.5 mol% or more based on the aromatic carboxylic acid and / or its ester. If the amount is less than this, an effective increase in the degree of polymerization cannot be obtained. The substantial upper limit of the amount of addition is about 10 mol%, and adding more than this is not preferable because the active ester compound added in the subsequent depressurization step is distilled off as it is. More preferably, it is in the range of 1 to 8 mol%.

Depending on the degree of increase in the degree of polymerization, multiple additions are possible. A major feature of this method is that it can be added repeatedly. Usually, the degree of polymerization of the present invention is reached in 2 to 5 additions. Regarding the method of adding the active ester compound, the active ester compound may be in the form of powder or melted and put into the polymerization system. More preferably, it is added in a molten state that enables uniform dispersion and mixing with the polymer.

The active ester compound thus added is subjected to the following reaction with the OH group at the terminal of the polymer present in the polymerization system, and then the phenol group and / or the ethylene carbonate are removed, and the polymer terminals are bonded to each other.
Reaction when diphenyl carbonate is used as the active ester compound in the following formula (a-1), and (a-2)
Shows the reaction when diphenylterephthalate is used as the active ester compound.

[0044]

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In the above formula, n is from 3 to 1,000, preferably from 10 to 800, more preferably from 20 to 600.

The phenol and / or ethylene carbonate generated by the reaction are quickly distilled out of the system by the same vacuum treatment as in the prior art.

The chemical structure introduced by these additives is exactly the same as that obtained by simply conducting the polymerization under reduced pressure, and almost no residual structure derived from the additives is observed in the polyetherester thus obtained. This is also a major feature of this manufacturing method.

The PBT resin (A) used in the present invention is generally a thermoplastic saturated polyester resin obtained by polycondensing terephthalic acid or a dialkyl terephthalate with 1,4-butanediol. .

The reduced viscosity, which indicates the degree of polymerization of a generally used PBT-based resin, has a concentration of 1.2 in a mixed solvent of phenol / tetrachloroethane (weight ratio 60/40).
(G / dl), 0.5 to 3.0 as measured at 35 ° C.
The range of dL / g is preferable, and the range of 1.0 to 2.0 dL / g is more preferable.

The PBT resin (A) used in the present invention is generally a thermoplastic saturated polyester resin obtained by polycondensation of terephthalic acid or a dialkyl terephthalate with 1,4-butanediol. .

The method for producing the resin is not particularly limited, and a resin produced by a known vacuum polycondensation method, a direct polycondensation method, or the like can be used.

In addition to the PBT resin, a thermoplastic resin may be contained in an amount of 1% by weight to 50% by weight.

Examples of the thermoplastic resin that can be used at that time include polycarbonate, polyethylene terephthalate, polynaphthalene terephthalate, PMMA resin, polystyrene resin, ABS resin, PP resin, and PPE resin.

The antistatic resin composition of the present invention comprises 5 to 30 parts by weight of the polyetherester (B) and 0 to 10 parts by weight of the surfactant (C) based on 100 parts by weight of the PBT resin (A) shown above. 0.5-6 parts by weight. Examples of such a surfactant include an anionic surfactant and a cationic surfactant. From the viewpoint of heat resistance required at the time of kneading with a polyetherester or the like, an anionic surfactant is preferable. . Even more surprisingly, by using an anionic surfactant such as an alkyl sulfonate or an alkylbenzene sulfonate as the anionic surfactant, such an antistatic effect is significantly increased, and the effect is permanent. To last. It is presumed that such a sulfonic acid salt contributes to the improvement of such an effect when used in combination with the acid component represented by the above formula (1), which constitutes the above polyetherester.

Examples of the alkyl sulfonate include sodium dodecyl sulfonate, potassium dodecyl sulfonate,
Examples thereof include sodium decyl sulfonate, potassium decyl sulfonate, sodium cetyl sulfonate, potassium cetyl sulfonate, and mixtures thereof. Examples of the alkylbenzene sulfonate include sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate, sodium decylbenzenesulfonate, potassium decylbenzenesulfonate, sodium cetylbenzenesulfonate, potassium cetylbenzenesulfonate and mixtures thereof. And the like.

The surfactant in the resin composition of the present invention is 0 to 100 parts by weight of the PBT resin (A) and 5 to 30 parts by weight of the polyetherester (B). 0.5-6 parts by weight. If the amount is less than 0.5 part by weight, the effect of adding the surfactant will not be exhibited, and if it exceeds 6 parts by weight, it may cause a decrease in physical properties or a decrease in handleability. The content of the surfactant (B) is preferably 0.7 to 5 parts by weight, more preferably 1 to 4 parts by weight.

The antistatic resin composition of the present invention is produced by melt-mixing the above PBT resin (A), polyetherester (B) and surfactant (C) by a conventionally known method. Can be. As a method of melt mixing, for example, such a component of the resin composition of the present invention,
There is a method of melt-mixing using a single-screw or twin-screw melt extruder.

The components (A) and (B) of the above resin composition
And (C) may be melt-mixed simultaneously, but the polyetherester (B) and the surfactant (C)
Is melt-mixed, and then melt-mixed with the PBT resin (A), thereby exhibiting a permanent antistatic effect, and exhibiting little reduction in transparency, physical properties, moldability and heat resistance. A PBT-based resin composition can be obtained, which is desirable.

As a method for previously melting and mixing the polyetherester (B) and the surfactant (C), for example, after the polyetherester has been polymerized, the surfactant is added to the polymerization tank and mixed. , Melt mixing with PBT resin (A), mixing polyetherester (B) and surfactant (C) using uniaxial or biaxial melt extruder and melt mixing with system resin (A) And the like. The temperature at which the polyetherester (B) and the surfactant (C) are melted and mixed is generally from 140 ° C to 300 ° C. If the temperature is lower than 140 ° C., mixing may not be sufficient, and if the temperature is higher than 300 ° C., deterioration such as decomposition may occur, which is not preferable. The melt mixing temperature is preferably from 160 ° C to 2
70 ° C, more preferably from 200 ° C to 260 ° C.

The mixture comprising (B) and (C) thus obtained is further mixed with PBT resin (A) at 200 ° C.
By melting and mixing at 00 ° C., the antistatic P
A BT-based resin composition can be obtained. Such mixing can be carried out using a single or twin screw melt extruder. At this time, if the temperature is lower than 200 ° C., mixing may not be sufficient, and if the temperature is higher than 300 ° C., deterioration such as decomposition may occur, which is not preferable. The melt mixing temperature is preferably from 220 ° C to 290 ° C, more preferably from 230 ° C to 280 ° C.

The antistatic PBT resin composition of the present invention comprises:
Various additives may be contained as needed. Examples of such additives include glass fiber, metal fiber, aramid fiber, ceramic fiber, potassium whisker, carbonate fiber, fibrous reinforcing agent such as asbestos, talc, calcium carbonate, mica, clay, titanium oxide, aluminum oxide, Various fillers such as glass flakes, milled fibers, metal flakes and metal powders, heat stabilizers such as phosphate esters and phosphites or catalyst deactivators, oxidation stabilizers, light stabilizers, lubricants And additives such as a pigment, a flame retardant, a flame retardant auxiliary, and a plasticizer.

Particularly, as the light stabilizer, the following formula (X)

[0063]

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A triazine-based light stabilizer as shown in (1) can be preferably used. Rx in the following formula (X) represents an alkyl group having 1 to 19 carbon atoms. Specifically, Rx
Is an n-hexyl group, 2- (4,6-diphenyl-
1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol (formula (X-1) below)

[0065]

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Can be preferably used. The compound is preferably added in an amount of 0.01 to 5% by weight, more preferably 0.1 to 1% by weight, based on 100 parts by weight of the polyetherester (B).

In particular, a hindered phenol-based oxidation stabilizer can be preferably used as the oxidation stabilizer. As a specific example, 1,3,5-trimethyl-2,4,
6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 3,9-bis [2- [3- (3-
t-butyl-4-hydroxy-5-methylphenyl)-
Propionyloxy] -1,1-dimethylethyl]-
Preferred compounds include 2,4,8,10-tetraoxaspiro [5.5] undecane. The compound is preferably added in an amount of 0.01 to 5% by weight, more preferably 0.1 to 1% by weight, based on 100 parts by weight of the polyetherester (B).

[0068]

According to the present invention, a polyetherester containing a specific aromatic dicarboxylic acid component nucleus-substituted with a sulfonate group and a surfactant are mixed with a PBT-based resin to form the mixture. It is possible to obtain a PBT-based resin composition that permanently exhibits a high antistatic effect without impairing the mechanical properties and the like of the PBT-based resin.

Accordingly, such a resin composition is useful for OA equipment, electronic members, automobile housings, medical members, various containers, covers, films, sheets and the like.

[0070]

EXAMPLES Preferred embodiments of the present invention will be described below with reference to examples, but the present invention is not limited to the examples. In the examples, "parts" means "parts by weight".
The reduced viscosity is a value measured at 35 ° C. at a concentration of 1.2 (g / dl) in a mixed solvent of phenol / tetrachloroethane (weight ratio 60/40) unless otherwise specified. The measurement of the surface resistivity was carried out by standing for 24 hours at 20 ° C. and a humidity of 60%, and then applying an applied voltage of 1000 using a super insulation meter (SM-8210 manufactured by Toa Denpa Kogyo Co., Ltd.).
V. The molded product was washed with running water at 30 ° C. for 2 hours, and the moisture was wiped off with clean paper. afterwards,
It dried under the same conditions and measured the surface specific resistivity.
The light fastness was evaluated by irradiating the polymerized chip with a mercury lamp for 40 hours. The reduction in reduced viscosity was 50% or less, “X”, 50% or more and 80% or less, “△”, and 80% or more. "O" was given. "Eye and eye" generation evaluation during molding
Evaluation was made by observing the strand discharge portion of the extruder at the time of chipping by the extruder described in the examples. That is, "x" indicates that a foreign substance colored like "eyes" was generated in the discharge section, and "o" indicates that no foreign substance was generated.

Reference Example 1 10418 parts of dimethyl terephthalate, 1865 parts of dimethyl 5-sodium sulfoisophthalate (10.5 mol%), 7440 parts of ethylene glycol, 26400 parts of polyethylene glycol (number average molecular weight 2000) ( 70% by weight), and 2
4.48 parts of tetrabutyl titanate was placed in a reactor equipped with a rectification column and a stirrer, and the atmosphere in the vessel was replaced with nitrogen.
The temperature was raised to 200 ° C. under normal pressure. After performing the reaction for 5 hours while distilling off methanol, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-) is used as a hindered phenol-based oxidation stabilizer. 189 parts of (hydroxybenzyl) benzene were added, and the reaction mixture was placed in a reactor having a vacuum distillation system equipped with a stirrer, and the reaction mixture was added for 23 minutes in 45 minutes.
The temperature was raised to 0 ° C. At that time, the pressure in the reaction system was gradually reduced to 0.3 mmHg after 60 minutes, the pressure was returned to normal after 2 hours, 154 parts of diphenyl carbonate was added, and the stirring under reduced pressure was restarted. Thereafter, the addition of diphenyl carbonate and the reduced pressure treatment were repeated every hour in the same manner as described above. After finishing the fourth decompression treatment, 2- (4,6-
Diphenyl-1,3,5-triazin-2-yl) -5
-[(Hexyl) oxy] -phenol: tinuvin 15
189 parts of 77ff (manufactured by Ciba Specialty Chemical Co., Ltd.) were added, mixed for 10 minutes, and discharged. The reduced viscosity of the polyetherester finally obtained was 3.92.

Reference Example 2 11095 parts of dimethyl terephthalate, 831 parts of dimethyl 5-sodium sulfoisophthalate (4.68 mol%), 7440 parts of ethylene glycol, 25080 parts of polyethylene glycol (number average molecular weight 2000) ( 30% by weight), and 24.
Forty-eight parts of tetrabutyl titanate was placed in a reactor equipped with a rectification tower and a stirrer, and the atmosphere in the vessel was replaced with nitrogen. 5 while distilling off methanol
After performing the reaction for 1 hour, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) is used as a hindered phenol-based oxidation stabilizer.
149 parts of benzene were added and the reaction was placed in a reactor having a vacuum distillation system equipped with a stirrer,
Temperature. At that time, the pressure inside the reaction system was gradually reduced to 6
The pressure was adjusted to 0.3 mmHg after 0 minute, the pressure was returned to normal after 2 hours, 154 parts of diphenyl carbonate was added, and the stirring under reduced pressure was restarted. Thereafter, the addition of diphenyl carbonate and the reduced pressure treatment were repeated every hour in the same manner as described above. After finishing the fifth pressure reduction, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- as a light stabilizer.
[(Hexyl) oxy] -phenol: tinuvin 157
149 parts of 7ff (manufactured by Ciba Specialty Chemical Co., Ltd.) was added, mixed for 10 minutes, and then discharged. The reduced viscosity of the finally obtained polyetherester was 4.57.

Reference Example 3 (without light stabilizer) 11095 parts of dimethyl terephthalate, 831 parts of 5
Dimethyl sodium sulfoisophthalate (4.68 mol%), 7440 parts of ethylene glycol, 25080
Parts of polyethylene glycol (number average molecular weight 2000)
(70% by weight) and 24.48 parts of tetrabutyl titanate were placed in a reactor equipped with a rectification tower and a stirrer. After the inside of the vessel was replaced with nitrogen, the temperature was raised to 200 ° C. under normal pressure.
After performing a reaction for 5 hours while distilling off methanol, 3,9-bis [2] was used as a hindered phenol-based oxidation stabilizer.
-[3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane Was added, and the reaction product was charged into a reactor having a vacuum distillation system equipped with a stirrer, and the temperature was raised to 230 ° C. in 45 minutes. At that time, the pressure in the reaction system was gradually reduced to 0.3 mmHg after 60 minutes, the pressure was returned to normal after 2 hours, 154 parts of diphenyl carbonate was added, and the stirring under reduced pressure was restarted. Thereafter, the addition of diphenyl carbonate and the reduced pressure treatment were repeated every hour in the same manner as described above.
After the fifth decompression process, the liquid was discharged. The reduced viscosity of the polyetherester finally obtained was 3.20.

Reference Example 4 (Low polymerization degree) 11095 parts of dimethyl terephthalate, 831 parts of 5
Dimethyl sodium sulfoisophthalate (4.68 mol%), 7440 parts of ethylene glycol, 25080
Parts of polyethylene glycol (number average molecular weight 2000)
(70% by weight) and 24.48 parts of tetrabutyl titanate were placed in a reactor equipped with a rectification tower and a stirrer. After the inside of the vessel was replaced with nitrogen, the temperature was raised to 200 ° C. under normal pressure.
After performing a reaction for 5 hours while distilling off methanol, 3,9-bis [2] was used as a hindered phenol-based oxidation stabilizer.
-[3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane Was added, and the reaction product was charged into a reactor having a vacuum distillation system equipped with a stirrer, and the temperature was raised to 230 ° C. in 45 minutes. At that time, the pressure in the reaction system was gradually reduced to 0.3 mmHg after 60 minutes, and the reaction was discharged after 8 hours. The reduced viscosity of the polyetherester finally obtained was 0.87.

[Examples 1, 2, and 3] 10 parts of the polyetherester obtained in Reference Examples 1 to 3 and dodecylbenzene as a surfactant were added to a PBT resin ("TRB-HT" manufactured by Teijin Limited). A mixture with 1 part of sodium sulfonate (100 parts in total) was added in an amount shown in Table 1 below,
Using a 30 mm φ co-rotating twin-screw extruder (PCM30, manufactured by Ikegai Iron Works Co., Ltd.), polymer temperature 25
The mixture was melt-kneaded at 0 ° C. and an average residence time of about 3 minutes, and pelletized. Next, using an injection molding machine (M-50B manufactured by Meiki Seisakusho Co., Ltd.), the cylinder temperature was set to 250 ° C.
Injection molding was performed at a mold temperature of 50 ° C. to obtain a molded product having a thickness of 2 mm, and the surface resistivity was measured. The results are shown in Table 1 together with the light fastness and the occurrence of "eye fray" during molding.

[Comparative Example 1] A mixture of the polyetherester and the surfactant obtained in Reference Example 4 with respect to 100 parts of a PBT resin ("TRB-HT" manufactured by Teijin Limited) is shown in Table 1 below. 30mmφ same direction rotation 2
Shaft extruder (PCM3 manufactured by Ikegai Iron Works Co., Ltd.)
Using 0), the mixture was melt-kneaded under the conditions of a polymer temperature of 250 ° C. and an average residence time of about 3 minutes, and pelletized. Next, using an injection molding machine (M-50B manufactured by Meiki Seisakusho Co., Ltd.), injection molding was performed at a cylinder temperature of 250 ° C. and a mold temperature of 50 ° C. to obtain a molded product having a thickness of 2 mm, and measurement of surface resistivity was performed. Was done. Table 1 shows the results together with mechanical properties and lightness index.
Shown in

[Comparative Example 2] PBT resin ("TRB-HT" manufactured by Teijin Limited) was molded using an injection molding machine (M-50B manufactured by Meiki Seisakusho Co., Ltd.) at a cylinder temperature of 250 ° C and a mold temperature of 50 ° C. , And a molded product having a thickness of 2 mm was obtained, and the surface resistivity was measured. The results are shown in Table 1 together with the mechanical properties.

[0078]

[Table 1]

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Claims (8)

[Claims] 1. 100 parts by weight of a PBT resin (A), a dicarboxylic acid having 6 to 20 carbon atoms and / or an ester thereof (B1), a poly (alkylene oxide) glycol having a number average molecular weight of 200 to 50,000 (B2), and Carbon number 2
In a resin composition comprising 5 to 30 parts by weight of a polyetherester (B) obtained by polycondensation of glycol (B3) of 10 to 10 and 0.5 to 6 parts by weight of a surfactant (C), ) Is the following formula (1) [In the formula (1), Ar is a trivalent aromatic group having 6 to 12 carbon atoms, R ¹ and R ² are each independently a hydrogen atom and 1 to 1 carbon atoms.
6 represents an alkyl group or an aryl group having 6 to 12 carbon atoms, and M ⁺ represents a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion. ]
The aromatic dicarboxylic acid and / or its ester (B1 ′) substituted with a sulfonic acid group represented by the formula (3) is contained in an amount of 3 to 50 mol% of the total acid component (B1), and the polyetherester (B) is formed. When the content of (B2) is (B
1) in the range of 40 to 90% by weight of the total amount of (B2) and (B3), and the polyetherester (B)
Is phenol / tetrachloroethane (weight ratio 60/4)
0) at 35 ° C. in a mixed solvent (concentration 1.
(2 g / dl), and not less than 1.0 and not more than 5.0. 2. The method according to claim 1, wherein the polyetherester (B) is an aromatic carboxylic acid and / or its ester (B) at the time of polycondensation.
2. The antistatic PBT resin composition according to claim 1, wherein the composition is obtained by adding 0.5 to 10 mol% of the active ester compound to 1). 3. The antistatic PBT resin composition according to claim 2, wherein the active ester compound is an aromatic ester derivative and / or an aromatic carbonate. 4. The antistatic PBT resin composition according to claim 2, wherein the active ester compound is diphenyl terephthalate and / or diphenyl carbonate. 5. The surfactant according to claim 1, wherein the surfactant (C) is at least one ionic surfactant selected from the group consisting of alkyl sulfonates and alkyl benzene sulfonates. Anti-static PBT resin composition. 6. The compound of the following formula (X) with respect to 100 parts by weight of the polyetherester (B). Wherein Rx represents an alkyl group having 1 to 19 carbon atoms in the formula (X), wherein a triazine light stabilizer represented by the formula: 0.01 to 5% by weight is contained. The antistatic PBT resin composition according to any one of the above. 7. The method according to claim 1, wherein the hindered phenol-based oxidation stabilizer is further contained in an amount of 0.01 to 5% by weight based on 100 parts by weight of the polyetherester (B). The antistatic PBT resin composition according to any one of the above. 8. The following formula (1): [In the formula (1), Ar is a trivalent aromatic group having 6 to 12 carbon atoms, R ¹ and R ² are each independently a hydrogen atom and 1 to 1 carbon atoms.
6 represents an alkyl group or an aryl group having 6 to 12 carbon atoms, and M ⁺ represents a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion. ]
And a dicarboxylic acid having 6 to 20 carbon atoms and / or an ester thereof (B) including an aromatic dicarboxylic acid and / or an ester thereof (B1 ′) substituted with a sulfonic acid group represented by
1), poly (alkylene oxide) glycol (B2) having a number average molecular weight of 200 to 50,000, and 2-1 to 2 carbon atoms
0 to 10 to 10 mol% based on the glycol (B3) and the dicarboxylic acid and / or ester thereof (B1).
And a polycondensation reaction to obtain a polyetherester (B), followed by melt-mixing the polyetherester (B) with the surfactant (C),
A method for producing an antistatic PBT resin composition, which is further melt-mixed with the PBT resin (A).