JP3453297B2 - Antistatic agent - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic agent which, when added to a thermoplastic resin, can impart excellent antistatic properties to the thermoplastic resin.

[0002]

2. Description of the Related Art A thermoplastic resin is liable to be significantly charged due to abrasion, peeling and the like, which causes various problems on a molded product, for example, impact due to discharge during use and adhesion of dust.

As a method of imparting antistatic properties to a thermoplastic resin, a phosphonium salt of an alkyl sulfonic acid (Japanese Patent Laid-Open No. 62-62160)
-230835) and a high molecular weight antistatic agent such as polyether ester amide are known.

The low-molecular type antistatic agent has a high initial effect, but its performance changes depending on environmental changes such as loss of antistatic property when wiped or washed. Also,
When applied to engineering plastics, polymeric antistatic agents often have problems in terms of heat resistance and melt stability.

It is already known to use a polyetherester type polymer type antistatic agent as a method for imparting permanent antistatic property (Japanese Patent Laid-Open No. 6-57153).

[0006]

However, it is difficult to impart sufficient antistatic properties to this conventional polyetherester type polymer antistatic agent when added to crystalline engineering plastics or the like. The present inventors have also found that when a known low-molecular type antistatic agent is used in combination with a jig for transportation in the field of electronics, the antistatic property may change in a water washing step or the like. The present invention aims to solve these problems. An object of the present invention is to provide an antistatic agent having excellent permanent antistatic property, heat resistance and melt stability.

[0007]

Means for Solving the Problems As a result of earnest studies, the present inventor has found that a specific polyetherester block copolymer excellent in compatibility with a thermoplastic resin, mechanical strength, heat resistance, and the like is identified as a polymer compound. The present inventors have found that by mixing an appropriate amount of a compound with which a metal ion interacts, a very excellent antistatic agent with little change due to washing treatment can be obtained, and the present invention has been accomplished.

That is, the present invention relates to (A) (a) an acid component consisting of 60 to 100 mol% of a terephthalic acid component and 40 to 0 mol% of an isophthalic acid component based on the total acid component, and (b) the following general formula (I) ) Represented by a poly (alkylene oxide) glycol component,

[0009]

[Chemical 2]

[Wherein X represents a substituent group -H, -CH ₃ ,
_{-CH 2 Cl, -CH 2 Br,} -CH 2 I or -CH ₂ O
CH ₃ and n and m are n ≧ 0, m ≧ 0 and 120 ≧ (n
+ M) ≧ 20. When m is 2 or more X
May be the same or different. The poly (alkylene oxide) glycol component may be a random copolymer itself or a block copolymer. ] (C) A polyether ester block copolymer composed of a glycol component composed of tetramethylene glycol 65 to 100 mol% and ethylene glycol 35 to 0 mol% based on all glycol components (excluding (B) component) And (B) 100 parts by weight of a polyether ester block copolymer having a copolymerization amount of 40 to 80% by weight of all glycol components (including (B) component), and (B) a polymer compound. 0.001 to 20 parts by weight of a compound in which a main chain or a side chain interacts with a metal ion, and (C) a metal salt of 0 to 10
It is an antistatic agent consisting of parts by weight. Hereinafter, the present invention will be described in detail.

[Polyetherester Block Copolymer] The polyetherester block copolymer (A) used in the present invention comprises (a) a terephthalic acid component of 60 to 100 mol% and an isophthalic acid component based on the total acid components. 40-0 mol
% Acid component, (b) poly (alkylene oxide) glycol component represented by the following general formula (I),

[0012]

[Chemical 3]

[Wherein, X is a substituent --H, --CH ₃ ,
_{-CH 2 Cl, -CH 2 Br,} -CH 2 I or -CH ₂ O
CH ₃ and n and m are n ≧ 0, m ≧ 0 and 120 ≧ (n
+ M) ≧ 20. When m is 2 or more X
May be the same or different. The poly (alkylene oxide) glycol component may be a random copolymer itself or a block copolymer. ] (C) Polyetherester block copolymer consisting of a glycol component consisting of tetramethylene glycol 65 to 100 mol% and ethylene glycol 35 to 0 mol% based on all glycol components (excluding (B) component) A polyether ester block copolymer in which the copolymerization amount of the component (b) is 40 to 80% by weight of the total glycol component (including the component (b)).

The tetramethylene glycol component in the polyether ester block copolymer (A) must be 65 mol% or more based on the total glycol component (excluding the component (b)). If the content of the tetramethylene glycol component is less than 65 mol%, the moldability will deteriorate.

In the polyether ester block copolymer (A), a dicarboxylic acid other than terephthalic acid or isophthalic acid, such as phthalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, or tricarboxylic acid, is used as the acid component (a). Meritic acid, pyromellitic acid, naphthalenedicarboxylic acid,
Cyclohexanedicarboxylic acid may be copolymerized.

When these components are copolymerized, the copolymerization amount is preferably less than 40 mol% based on the total acid component amount,
More preferably, it is less than 20 mol%.

In the polyether ester block copolymer (A), as a glycol component (c), a diol other than tetramethylene glycol or ethylene glycol, for example, trimethylene glycol, 1,5-pentanediol, 1,6-hexane. Diol, diethylene glycol, 1,
4-Cyclohexanediol and 1,4-cyclohexanedimethanol may be copolymerized.

When these components are copolymerized, the copolymerization amount is preferably less than 40 mol%, more preferably 2 mol% based on the total amount of glycol components (excluding the component (b)).
It is less than 0 mol%.

The polyether ester block copolymer (A) is copolymerized with a poly (alkylene oxide) glycol component (b). The copolymerization amount of this (b) component is the total glycol component (however, B) Including ingredients) 40
-80% by weight, preferably 40-70% by weight. 40% by weight
If the amount is less than the above range, the effect of antistatic property is small, and if the amount exceeds 80% by weight, polymer fusion and sticking occur and problems occur in the process.

[0020]

[Chemical 4]

In the above formula (I), X is a hydrogen atom (-
H) or a substituent _{-CH 3, -CH 2 Cl, -CH} 2 Br,
Represents a -CH ₂ I or -CH ₂ OCH _3.

When X is a complex group other than these, it is difficult to increase the degree of polymerization of the copolymer due to steric hindrance. A polyethylene glycol unit whose main chain is directly substituted with halogen or an alkoxy group has a strong polymer degradability. X is preferably a hydrogen atom.

In the formula (I), n and m are n ≧ 0 and m ≧.
It is necessary to satisfy 0 and 120 ≧ (n + m) ≧ 20.
When the value of (n + m) is less than 20, the block property of the block copolymer is deteriorated and the antistatic property becomes insufficient. On the other hand, when the value of (n + m) is more than 120, the degree of polymerization is decreased and sufficient. Not only is it difficult to obtain a copolymer having a degree of polymerization, but also the antistatic property is reduced. When m is 2 or more, X may be the same or different.

The poly (alkylene oxide) glycol component (b) may be a random copolymer or a block copolymer.

[Compound in which polymer compound interacts with metal ion] The compound (B) in which the metal ion interacts with the main chain or side chain of the polymer compound used in the present invention is, for example, polyacryl. An acid salt or an ionomer of an ethylene / unsaturated carboxylic acid copolymer, preferably an ionomer of an ethylene / unsaturated carboxylic acid copolymer.

Here, the ionomer of the ethylene / unsaturated carboxylic acid copolymer means a random copolymer of ethylene and unsaturated carboxylic acid, or a random copolymer of ethylene / unsaturated carboxylic acid and other copolymerizable monomers. It is an ionomer of a copolymer.

The polymerization ratio of the unsaturated carboxylic acid in the random copolymer is usually 5 to 30% by weight, preferably 10
The amount of the other copolymerizable monomer is usually 0 to 40% by weight, preferably 0 to 25% by weight, and more preferably 0 to 10% by weight.

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, monomethyl maleate, monoethyl maleate, maleic anhydride, and itaconic acid, with acrylic acid or methacrylic acid being particularly preferred. Examples of other copolymerizable monomers include methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, isooctyl acrylate, methyl methacrylate, isobutyl methacrylate,
Unsaturated carboxylic acid esters such as diethyl maleate,
Vinyl acetate, vinyl ester such as vinyl propionate, carbon monoxide, etc., and acrylic acid and methacrylic acid esters are particularly preferable.

In the ionomer, the metal ion is
For example, zinc, magnesium, calcium, barium, sodium, potassium, lithium, lead, tin, aluminum, copper, cobalt, nickel. Particularly, potassium, sodium or magnesium is preferable.

The ionomer is neutralized with these metal ions, and the degree of neutralization of the ionomer with these metal ions is usually 5 to 100%, preferably 20 to 80%.

As the above-mentioned ionomer, 190
Melt flow rate under load of 2160g at 0.01-2
It is recommended to use one having a weight of 0 g / 10 minutes, preferably 0.1 to 10 g / 10 minutes.

Compound (B) in which the main chain or side chain of the polymer compound used in the present invention interacts with a metal ion
The compounding amount of the polyether ester block copolymer 10
It is 0.001 to 20 parts by weight with respect to 0 parts by weight. Preferably,
0.01 to 10 parts by weight. If the amount is less than 0.001 part by weight, there is no sufficient antistatic effect. If it is more than 20 parts by weight, the effect of improving the antistatic property is saturated, and when it is used as a container in the electronics field, it is not preferable because it may cause metal contamination in the washing step.

Thus, the compound obtained by compounding the ionomer with the polyether ester block copolymer in an appropriate amount causes less outflow of metal ions by washing with water, as compared with the combination of the low molecular weight antistatic agent and the polyether ester.
It can have extremely stable permanent antistatic properties.

[Metal Salt] The metal salt (C) used in the present invention
Is preferably a metal salt such as KCl or NaCl or a sulfonic acid metal salt. As the sulfonic acid metal salt, sodium dodecylbenzene sulfonate and potassium dodecyl sulfonate are preferable.

The amount of the metal salt (C) used in the present invention is 0 to 10 parts by weight based on 100 parts by weight of the polyetherester block copolymer. Addition of 10 parts by weight or more is not preferable because it causes the surface to be rough and coloring.

Various additives can be added to the antistatic agent used in the present invention within a range not impairing the object of the present invention.

Examples of the additives include releasing agents such as montanic acid wax, polyethylene wax and silicone oil, flame retardants, flame retardant aids, heat stabilizers, ultraviolet absorbers, pigments and dyes.

Further, other thermoplastic resins such as polyethylene, polypropylene, polystyrene, acrylic resin, fluorine resin, polyamide, polyacetal, polysulfone, polyphenylene sulfide; thermosetting resins such as phenolic resin within the range not impairing the object of the present invention. , Melamine resin, silicone resin, epoxy resin; soft thermoplastic resin such as ethylene / vinyl acetate copolymer, polyester elastomer, epoxy-modified polyolefin, and other fillers such as talc, kaolin, wax. Rastonite, clay, silica, sericite, titanium oxide, carbon black, graphite, metal powder, glass beads, glass balloons, glass flakes,
Glass powder and glass fiber can be added.

[Method for Producing Antistatic Agent] The electrostatic agent of the present invention can be obtained by blending the components (A), (B) and (C) by any blending method.

Usually, it is preferable to disperse these blending components more uniformly, and it is preferable to disperse all or part of them simultaneously or uniformly.

In the electrostatic agent of the present invention, a method in which all or a part of the components are simultaneously or separately mixed with a mixer such as a blender, a kneader, a Panbury mixer, a roll or an extruder and homogenized is used. Can be done.

Further, a method may be used in which the composition dry-blended in advance is melt-kneaded by a heated extruder, homogenized, extruded into a wire shape, and then cut into a desired length and granulated.

The antistatic agent of the present invention can be added to various resins to impart excellent antistatic properties to the resin composition. The resin composition imparted with antistatic property by the antistatic agent of the present invention is an antistatic film, an antistatic sheet, an antistatic plate, an IC tray, a package of an IC tray, an antistatic tape, a copying machine part, a charge for cathode ray tubes. Used for various applications such as anti-coating material, OA / communication equipment housing material, clean room interior material, silicon wafer carrier, silicon wafer carrier box, silicon wafer retainer bar, liquid crystal substrate carrier, HDD and LCD related parts carrier jig. It is possible. Hereinafter, the present invention will be described in more detail with reference to Examples.

[0044]

[Examples] The raw materials and evaluation methods used in the examples are as follows.

1. Raw materials: The following raw materials were used.

Polyether ester block copolymers 1 to 4 dimethyl terephthalate, dimethyl isophthalate, tetramethylene glycol, ethylene glycol, and (modified) polyethylene glycol so as to have the composition shown in Table 1, and tetrabutyl as a catalyst. Titanate (0.090 mol% based on the acid component) was charged into the reactor, and the internal temperature was 190 ° C.
The esterification reaction was carried out. After about 80% of the theoretical amount of methanol had been distilled, the temperature was started to increase and the polycondensation reaction was carried out while gradually reducing the pressure. After reaching a vacuum of 1mmHg or less, 240 ℃
The reaction was continued for 200 minutes. Next, the antioxidant Irganox 1010 was added to the polyethylene glycol or modified polyethylene glycol in an amount of 5% by weight to complete the reaction. The composition of the purified polymer is shown in Table 2. What was used in the examples is the copolymer obtained in Synthesis Example 1. Hereinafter, the copolymer obtained in Synthesis Example 1 is referred to as TRB-EKV in the table.

[0047]

[Table 1]

[0048]

[Table 2]

[0049] ・ Sodium dodecylbenzene sulfonate                       Takemoto Yushi Co., Ltd. TPL456 ・ Potassium ionomer (The ion-crosslinking of ethylene-methacrylic acid copolymer with potassium ions between the molecules Nomar)                       High milan MK153 manufactured by Mitsui / Duphon Polychemical Co., Ltd.                       MFR 0.50 (g / 10 minutes)                       Melting point 93 (℃) ・ Potassium chloride (KCl)                       Wako Pure Chemical Industries, Ltd.                       JIS reagent special grade

2. Antistatic property (resistivity, saturated electrification voltage and electrification half-decay time): Antistatic property is an applied voltage of 10 KV (distance between sample electrodes, measured by an Honest meter (Static H-0110 manufactured by Shishido Electrostatic Co., Ltd.) : 20m
It was evaluated by the saturated electrification voltage and the electrification voltage half decay time in m) and the surface resistivity measured using a super insulation meter (SM-10E manufactured by Toa Denpa Kogyo KK). The half-decay time and the surface resistivity were measured at a temperature of 23 ° C. and a relative humidity of 50% after conditioning the sample for 24 hours in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%.

3. Washing with water: Hand-wash the surface with a sponge for 3 minutes using a neutral detergent (water solution of Mama Lemon: 1.5 ml / L), and wash with warm pure water (60 ° C) for 3 minutes, and air-blow the sample surface to 80 ° C 10 Oven dried for minutes. This washing process is repeated 3 times and the final drying is 80
℃, vacuum, 12 hours, then 23 ℃, 50% RH 2
The condition was conditioned for 4 hours.

[Examples 1 to 5 and Comparative Examples 1 and 2] Various raw materials were preliminarily uniformly dry blended in the proportions (parts by weight) shown in Tables 3 and 4, and then a screw diameter 44 mm with a vent 2 Cylinder temperature 210-250 using a shaft extruder
Degree, screw rotation speed 160-220 rpm, discharge rate 50 kg /
After melt-kneading at h, the thread discharged from the die was cooled and cut to obtain molding pellets. Then, using this pellet, an injection pressure of 750 kg / cm ² and an injection speed of 70
cm ³ / sec, cooling time 15 seconds, and total molding cycle 25 seconds by injection molding a disc test piece (diameter 50 mm,
3mm thick) was created. The evaluation results are shown in Tables 3 and 4.

[0053]

[Table 3]

[0054]

[Table 4]

As shown in Table 3, as compared with the polyether ester alone system (Comparative Example 1), the one containing potassium ionomer (Examples 1 and 4) showed a surface resistivity lower by an order of magnitude and an applied voltage of 10 KV. It showed very good antistatic property with almost no charge even when a voltage was applied. This tendency hardly changes even after annealing. Furthermore, TPL456 and K
Good results were obtained even when Cl was used together (Example 2,
3).

As shown in Table 4, polyetherester +
Unlike the conventional formulation (Comparative Example 2), the potassium ionomer system (Example 5) does not change its effect even when subjected to a very strict washing test.

[0057]

According to the present invention, it is possible to provide an antistatic agent having excellent permanent antistatic property, heat resistance and melt stability.

Claims (4)

(57) [Claims] 1. A) (a) 60 to 100 mol% of terephthalic acid component and 40 to 0 m of isophthalic acid component based on the total acid components
an acid component consisting of ol%, (b) a poly (alkylene oxide) glycol component represented by the following general formula (I), [Wherein, X represents a substituent —H, —CH ₃ , —CH ₂ Cl,
Represents —CH ₂ Br, —CH ₂ I or —CH ₂ OCH ₃ ,
It is assumed that n and m satisfy n ≧ 0, m ≧ 0 and 120 ≧ (n + m) ≧ 20. When m is 2 or more, X may be the same or different. The poly (alkylene oxide) glycol component may be a random copolymer itself or a block copolymer. ] (C) Polyetherester block copolymer consisting of a glycol component consisting of tetramethylene glycol 65 to 100 mol% and ethylene glycol 35 to 0 mol% based on all glycol components (excluding (B) component) And (B) 100 parts by weight of a polyether ester block copolymer having a copolymerization amount of 40 to 80% by weight of all glycol components (including (B) component), and (B) a polymer compound. 0.001 to 20 parts by weight of a compound in which a main chain or a side chain interacts with a metal ion, and (C) a metal salt of 0 to 10
Antistatic agent consisting of parts by weight. 2. The antistatic agent according to claim 1, wherein the compound (B) in which the main chain or side chain of the polymer compound interacts with the metal ion is an ionomer of an ethylene / unsaturated carboxylic acid copolymer. . 3. The metal ion constituting the ionomer (B) of the ethylene / unsaturated carboxylic acid copolymer is zinc, magnesium, calcium, barium, lead, tin, sodium, potassium, lithium, aluminum, copper, cobalt, The antistatic agent according to claim 2, which is one or more metal ions selected from the group consisting of nickel. 4. The antistatic agent according to claim 1, wherein the metal salt (C) is one or more metal salts selected from the group consisting of KCl, NaCl, sodium dodecylbenzenesulfonate and potassium dodecylsulfonate.