JP2928380B2 - Permanent antistatic resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an antistatic resin composition having excellent permanent antistatic properties. Applications include electronic components, ICs
The present invention relates to an antistatic resin composition suitable for chips, food containers, various dustproof bodies and molded articles, carrier tapes, packaging bags, trays, floppy disks, containers for storing electronic materials, and the like.

(Prior art and problems) Conventionally, electronic parts, such as electronic parts, which dislike static electricity, are stored in a container containing carbon or metal fine powder. There is a drawback such as contamination. In order to combine antistatic properties and transparency, simply apply an antistatic agent to the resin,
When kneaded, the antistatic agent bleeds out of the antistatic agent and contaminates the contents, and the antistatic property deteriorates over time.

(Means for Solving the Problems) In order to solve these problems, the present inventors have developed a vinyl aromatic compound-conjugated diene compound block copolymer and a block copolymer having excellent moldability and transparency. Focusing on possible lactone compounds, as a result of repeated research, antistatic properties and permanent electrification by combining a resin composition of a block copolymer in a specific composition range with a specific styrene resin and an antistatic agent It was found that it was excellent in prevention.

That is, the present invention is a block copolymer comprising a polymer block composed of a vinyl aromatic compound and a polymer block composed of a conjugated diene compound and a polymer block composed of a lactone compound, wherein the vinyl aromatic compound content Is 10 to 100% by weight, the content of the conjugated diene compound is 0 to 90% by weight, and the sum of the vinyl aromatic compound and the conjugated diene compound is 30 to 59% by weight, and the lactone compound is 70 to 41% by weight. % Block copolymer, a general type styrene resin, a styrene-bradiene graft copolymer resin, a styrene-isoprene block copolymer resin,
Styrene-butadiene-based block copolymer resin and a resin selected from hydride of the copolymer resin and resin composition 100
It is characterized by a permanent antistatic resin composition comprising parts by weight and 0.1 to 2.0 parts by weight of an antistatic agent.

 Hereinafter, the present invention will be described in more detail.

The block copolymer used in the present invention is obtained by copolymerizing a polymer block composed of a vinyl aromatic compound and a polymer block composed of a conjugated diene compound and a polymer block composed of a lactone compound. Is 10 to 100% by weight, the content of the conjugated diene compound is 0 to 90% by weight, the sum of the vinyl aromatic compound and the conjugated diene compound is 30 to 59% by weight, and the lactone compound is
What is 70-41% by weight is used.

When the content of the vinyl aromatic compound is less than 10% by weight, the moldability is poor when the block copolymer is used alone, and the compatibility with the styrene-based resin is poor, causing a layer peeling phenomenon.

The lactone content in the block copolymer was 41% by weight.
If less, the effect of preventing the antistatic property from changing with time is inferior, and
When the content exceeds 70% by weight, the heat resistance of the lactone-based compound decreases due to the melting point.

Next, the structure and connection type of the block copolymer will be described.

The structural type of the block copolymer used in the present invention is:
(AB) nC, (AB) nA-C, X [(AB) nA-
Any type such as C] m and X [(AB) nC] m may be used. Here, A represents a polymer chain composed of a vinyl aromatic compound, B represents a polymer chain composed of a conjugated diene compound, C represents a polymer chain composed of a lactone compound, n represents an integer of 1 to 20, and m represents an integer. Represents an integer of 3 to 7.
X represents a polyfunctional compound linking m polymer chains.

Furthermore, the connection form of the block connection portion comprising the vinyl aromatic compound and the conjugated diene compound used in the present invention is as follows:
It may be a so-called clear-cut structure in which both components of a vinyl aromatic compound and a conjugated diene compound are mixed, that is, one or more include a so-called tapered structure, or both components are not mixed at all.

The block copolymer used in the present invention may be a mixture of two or more block copolymers having different molecular weights, and may have different contents of the vinyl aromatic compound and the conjugated diene compound. A mixture of two or more block copolymers may be used. Furthermore, the block copolymer used in the present invention may be a mixture of two or more different lactone compounds.

Next, the types of each compound in the block copolymer will be described.

First, the vinyl aromatic compound used in the present invention includes styrene, α-methylstyrene, p-methylstyrene, vinyltoluene and the like, and styrene is a typical example. The conjugated diene compound used in the present invention includes butadiene and isoprene, and a typical example is butadiene.

Further, as the lactone compound used in the present invention,
There is no particular limitation as long as a block copolymer can be formed with the vinyl aromatic compound and the conjugated diene compound, but β-ε lactone compounds represented by the general formula are preferred. General formula (Where R ₁ , R ₂ and R ₃ are H or an alkyl group of C _{1 to} C ₈ , and n represents an integer of 1 to 5), specifically, β-propiolactone, Dimethylpropiolactone (pivalolactone), butyrolactone, γ-valerolactone, γ-caprolactone, γ-caprylolactone, γ-laurolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, and the like, preferably ε-caprolactone. Caprolactone and dimethylpropiolactone.

Next, the resin mixed with the block copolymer of the present invention is a general type styrene resin, a styrene-butadiene graft copolymer resin, a styrene-butadiene block copolymer resin, a styrene-isoprene block copolymer resin, and the block copolymer. The hydride of each resin (hereinafter referred to as styrene resin).

The ratio of the block copolymer of the present invention to the styrene resin is preferably such that the block copolymer is used in the range of 90 to 10% by weight and the styrene resin in the range of 10 to 90% by weight. Exceeds 90% by weight, the effect of the antistatic property is reduced.

 Next, types of the antistatic agent will be described.

"New Edition Surfactant Handbook" (Tokiyuki Yoshida et al .: 198
According to 7.10.1 issue, Engineering Books Co., page 351)
Kneading type antistatic agent mixed with plastic (internal a
ntistatic agents) are generally selected from surfactants,
It is described that the incorporated surfactant is transferred to the plastic surface after molding to form a thin film. The antistatic property is widely used as a means for evaluating the antistatic property, and it is described that the antistatic property has an antistatic property when the surface specific resistance is 10 ¹² Ω or less, and is fairly good when the surface specific resistance is 10 ⁹ Ω or less. Have been.

In the present invention, "antistatic agent" refers to an antistatic agent selected from surfactants having a surface resistivity of 10 ¹² Ω or less as described in this description, and specific types of antistatic agents. As the nonionic, cationic, anionic, quaternary amine antistatic agents, and as typical examples,
There are alkyl polyoxyethylene amines and sorbitan esters. The proportion of the antistatic agent is 0.1 to 2.0 parts by weight, preferably 0.1 to 1.0 part by weight, and more preferably 0.3 to 1.0 part by weight based on 100 parts by weight of the resin composition. If the proportion of the antistatic agent is less than 0.1 part by weight, the antistatic effect of the molded article is not satisfied, and if it exceeds 2.0 parts by weight, the surface of the molded article or the like bleeds, which is not preferable.

The permanent antistatic resin composition of the present invention has a surface specific resistance value of 10 ^{9 of the} surface of a molded article molded using the resin composition.
In the range of to 10 ¹² Omega, yet the range of surface resistivity even after water washing immediately after molding is 10 ⁹ ~10 ¹² Ω.

Further, as a method for obtaining a resin composition of the block copolymer of the present invention, a styrene-based resin and an antistatic agent, three components of the block copolymer, the styrene-based resin and the antistatic agent are mixed, and the mixture is extruded. A method of forming a uniform pellet, a method of obtaining a uniform resin composition of a block copolymer and a styrene-based resin, and further mixing an antistatic agent to make a uniform pellet, a method of forming a block copolymer and an antistatic agent After obtaining a uniform resin composition, a method of further mixing a styrene resin to form uniform pellets may be used.

Unlike the conventional antistatic resin, the resin composition of the block copolymer of the present invention, a styrene resin, and an antistatic agent hardly causes a decrease in antistatic properties due to wiping.

Applications of the antistatic resin composite material of the present invention include containers for storing IC chips, carrier tapes, packaging bags, shrink films, trays, floppy disk cases, various dustproof bodies and molded instruments, electronic material storage cases, and the like. There is.

As described above, the present invention can provide a resin composition having excellent antistatic properties and permanent antistatic properties.

(Examples) Hereinafter, the present invention will be described in detail with reference to examples. In addition, wt% in the table represents weight%, and PHR represents an added part by weight per 100 parts by weight of the block copolymer or the resin composition.

Example 1 60% by weight of a block copolymer having a styrene content of 40% by weight, a butadiene content of 10% by weight and an ε-caprolactone content of 50% by weight produced by the method (a) shown below and a general type styrene resin (electric Denkastyrol GP-PS, manufactured by Chemical Industry Co., Ltd., referred to as GP-PS) (40% by weight), 0.24 part by weight of a hindered phenol-based antioxidant, 0.30 part by weight of a phosphorus-based antioxidant, and 0.06% by weight of a fatty acid ester-based lubricant Antistatic agent composed of polyoxyethylene alkylamine and polyoxyethylene alkylamine (trade name: Electrostripper E, manufactured by Kao Corporation)
A, hereinafter referred to as antistatic agent EA) 1.0 part by weight
It was extruded with a mmφ extruder to produce uniform pellets.

Next, the obtained pellet is 10 cm x 10 c with a 2 oz injection molding machine.
An mx 2 mm square plate was molded, and the transparency, surface resistivity and strength of the molded product were evaluated. The results are shown in Table 1.

The transparency, the antistatic property, and the retention of the antistatic property by wiping were all good.

(A) Production method of block copolymer Purified benzene 75 in an autoclave having a capacity of 100
And styrene (4.0 kg) were charged and stirred. Then temperature 30
0.24 mol of n-butyl lithium at 40 ° C. and 30
A minute reaction was carried out to complete the polymerization. Next, butanediene 2.0k
g was charged and the temperature was raised to complete the polymerization. Then styrene
4.0 kg was charged and the temperature was raised to complete the polymerization. Next, ε-
40 g of caprolactone was charged and reacted at a temperature of 60 ° C. for 10 minutes, and 9.96 kg of ε-caprolactone was further charged and charged at 60 ° C. for 60 minutes.
A minute reaction was carried out to complete the polymerization. Finally, after removing benzene by steam distillation, the polymer slurry was dehydrated and dried.

Example 2 10% by weight of the block copolymer prepared in Example 1 and GP-
Hindered phenolic antioxidant is added to PS90% by weight.
04 parts by weight, 0.05 parts by weight of a phosphorus-based antioxidant, 0.02 parts by weight of a fatty acid ester-based lubricant and 1.0 part by weight of an antistatic agent EA were mixed, and uniform pellets were produced with a 40 mmφ extruder.

Next, using the obtained pellets, the same operation as in Example 1 was performed to measure the physical properties. The results are shown in Table 1.

The transparency, the antistatic property, and the retention of the antistatic property by wiping were all good.

Example 3 30% by weight of the block copolymer produced in Example 1 and 70% by weight of a styrene-butadiene graft copolymer resin (manufactured by Denki Kagaku Kogyo KK, Denkastyrol HI-S-2, hereinafter referred to as HI-PS) In addition, 0.12 parts by weight of a hindered phenolic antioxidant, 0.15 parts by weight of a phosphorus-based antioxidant, 0.05 parts by weight of a fatty acid ester-based lubricant and 1.0 part by weight of an antistatic agent EA are mixed, and uniformly mixed with a 40 mmφ extruder. Pellets were produced.
Next, using the obtained pellets, the same operation as in Example 1 was performed to measure the physical properties.

 The results are shown in Table 1.

Both the antistatic property and the retention of the antistatic property by wiping were good.

Example 4 10% by weight of the block copolymer prepared in Example 1 and HI-
Hindered phenolic antioxidant is added to PS90% by weight.
04 parts by weight, 0.05 parts by weight of a phosphorus-based antioxidant, 0.02 parts by weight of a fatty acid ester-based lubricant and 1.0 part by weight of an antistatic agent EA were mixed, and uniform pellets were produced with a 40 mmφ extruder. Next, using the obtained pellets, the same operation as in Example 1 was performed to measure the physical properties. The results are shown in Table 1.

Both the antistatic property and the retention of the antistatic property by wiping were good.

Example 5 50% by weight of the block copolymer prepared in Example 1 and GP-
25% by weight of PS and 25% by weight of HI-PS, 0.20 part by weight of a hindered phenolic antioxidant, and 0.25 part of a phosphorus-based antioxidant
Parts by weight, 0.08 parts by weight of fatty acid ester lubricant and antistatic agent
The mixture was mixed with 1.0 parts by weight of EA, and uniform pellets were produced using a 40 mmφ extruder. Next, using the obtained pellets, the same operation as in Example 1 was performed to measure the physical properties. Table-
1 is shown. Both the antistatic property and the retention of the antistatic property by wiping were good.

Example 6 20% by weight of the block copolymer prepared in Example 1, 80% by weight of a styrene-butadiene-based block copolymer resin (Clearen 730L, manufactured by Denki Kagaku Kogyo KK, hereinafter referred to as SBS block copolymer resin) and hinder Mix 0.08 parts by weight of dophenolic antioxidant, 0.10 part by weight of phosphorus antioxidant, 0.03 part by weight of fatty acid ester lubricant and 1.0 part by weight of antistatic agent EA, and form uniform pellets with a 40 mmφ extruder. Manufactured. Next, using the obtained pellets, the same operation as in Example 1 was performed to measure the physical properties.

 The results are shown in Table 1.

Both the antistatic property and the retention of the antistatic property by wiping were good.

Example 7 30% by weight of the block copolymer produced in Example 1 and a styrene content of 75 produced by the method (b) shown below
70% by weight of styrene-isoprene-based block copolymer resin (hereinafter referred to as SIS) with 25% by weight and isoprene content of 25% by weight
And 0.12 parts by weight of a hindered phenolic antioxidant, 0.15 part by weight of a phosphorus-based antioxidant, 0.05 part by weight of a fatty acid ester-based lubricant and 1.0 part by weight of an antistatic agent EA, and the mixture is uniformly pelletized with a 40 mmφ extruder. Was manufactured.

Next, using the obtained pellets, the same operation as in Example 1 was performed to measure the physical properties. The results are shown in Table 1.

Both the antistatic property and the retention of the antistatic property by wiping were good.

(B) Method for producing block copolymer Purified benzene 75 in an autoclave having a capacity of 100
And styrene (7.5 kg) were charged and stirred. Then temperature 30
0.24 mol of n-butyl lithium at 40 ° C. and 30
A minute reaction was carried out to complete the polymerization. Next, 5.0 kg of isoprene
And the temperature was raised to complete the polymerization. Then styrene 7.
5 kg was charged and the temperature was raised to complete the polymerization. Finally, after removing benzene by steam distillation, the polymer slurry was dehydrated and dried.

Example 8 50% by weight of the block copolymer produced in Example 1 and a hydride of a styrene-butadiene-based block copolymer resin (TAFTEC H1041, manufactured by Asahi Kasei Kogyo Co., Ltd .; hereinafter, referred to as SEBS) 5
0% by weight, 0.20 parts by weight of a hindered phenolic antioxidant, 0.25 parts by weight of a phosphorus-based antioxidant, 0.08 parts by weight of a fatty acid ester-based lubricant and 1.0 part by weight of an antistatic agent EA
Uniform pellets were produced with an mφ extruder.

Next, the same operations as in Example 1 were performed using the obtained pellets, and the physical properties were measured. The results are shown in Table 1.

Both the antistatic property and the retention of the antistatic property by wiping were good.

Example 9 40% by weight of the block copolymer produced in Example 1, 60% by weight of a hydride of a styrene-isoprene-based block copolymer resin (KL-2023 manufactured by Kuraray Co., Ltd., hereinafter referred to as SEPS), and a hindered phenol-based resin 0.16 parts by weight of antioxidant, 0,20 parts by weight of phosphorus-based antioxidant 0.06 parts by weight of fatty acid ester-based lubricant and 1.0 part by weight of antistatic agent EA are mixed, and uniformly mixed with a 40 mmφ extruder to form pellets. Manufactured.

Next, using the obtained pellets, the same operation as in Example 1 was performed to measure the physical properties. The results are shown in Table 1.

Both the antistatic property and the retention of the antistatic property by wiping were good.

Example 10 Styrene content produced in the method for producing a block copolymer shown in Example 1 by changing the following point (c).
35% by weight, 10% by weight of a block copolymer having a content of 5% by weight of butadiene and 60% by weight of ε-caprolactone and GP
-90% by weight of PS and hindered phenolic antioxidant
0.04 parts by weight, 0.05 parts by weight of a phosphorus-based antioxidant, 0.02 parts by weight of a fatty acid ester-based lubricant and 1.0 part by weight of an antistatic agent EA were mixed to produce uniform pellets at 4 mmφ. Next, using the obtained pellets, the same operation as in Example 1 was performed to measure the physical properties. The results are shown in Table-2.

Both the antistatic property and the antistatic property by wiping were good.

(C) Method for producing block copolymer Purified benzene 75 in an autoclave having a capacity of 100
And 3.5 kg of styrene were charged and stirred. Then temperature 30
0.24 mol of n-butyl lithium at 40 ° C. and 30
A minute reaction was carried out to complete the polymerization. Next, butadiene 1.0kg
And the temperature was raised to complete the polymerization. Then styrene 3.
5 kg was charged and the temperature was raised to complete the polymerization. Next, 40 g of ε-caprolactone was reacted at a temperature of 60 ° C. for 10 minutes, and 11.96 kg of ε-caprolactone was further charged at 60 ° C. for 6 minutes.
The reaction was carried out for 0 minutes to complete the polymerization. Finally, after removing benzene by steam distillation, the polymer slurry was dehydrated and dried.

Example 11 Styrene content produced in the method for producing a block copolymer shown in Example 1 by changing the following point (d).
50% by weight, 10% by weight of a block copolymer having a butanediene content of 5% by weight and an ε-caprolactone content of 45% by weight;
Mix 90% by weight of GP-PS, 0.04 part by weight of a hindered phenolic antioxidant, 0.05 part by weight of a phosphorus-based antioxidant, 0.02 part by weight of a fatty acid ester-based lubricant and 1.0 part by weight of an antistatic agent EA, and at 40 mmφ. Uniform pellets were produced. Next, using the obtained pellets, the same operation as in Example 1 was performed to measure the physical properties. The results are shown in Table-2.

Both the antistatic property and the antistatic property by wiping were good.

(D) Production method of block copolymer Purified benzene 75 in an autoclave having a capacity of 100
And 5.0 kg of styrene, and stirred. Then temperature 30
0.24 mol of n-butyl lithium at 40 ° C. and 30
A minute reaction was carried out to complete the polymerization. Next, butadiene 1.0kg
And the temperature was raised to complete the polymerization. Then styrene 5.
0 kg was charged and the temperature was raised to complete the polymerization. Next, 40 g of ε-caprolactone was charged and the reaction was carried out at 60 ° C. for 10 minutes, and 8.96 kg of ε-caprolactone was further charged at 60 ° C. for 60 minutes.
A minute reaction was carried out to complete the polymerization. Finally, after removing benzene by steam distillation, the polymer slurry was dehydrated and dried.

Example 12 10% by weight of the block copolymer prepared in Example 1 and GP
-90% by weight of PS and hindered phenolic antioxidant
0.04 parts by weight, phosphorus-based antioxidant 0.05 parts by weight, fatty acid ester-based lubricant 0.02 parts by weight, and an antistatic agent (Rikemar O-71-DE, manufactured by Riken Vitamin Co., Ltd.) containing polyglycene fatty acid ester as a component 1.0 part by weight. Were mixed, and uniform pellets were produced with a 40 mmφ extruder. The same operation as in Example 1 was performed using the obtained pellets, and the physical properties were measured. The results are shown in Table-2.

All of the transparency, the antistatic property, and the antistatic property by wiping were good.

Example 13 30% by weight of the block copolymer prepared in Example 1 and HI
-PS70% by weight and hindered phenolic antioxidant
0.12 parts by weight, 0.15 parts by weight of a phosphorus-based antioxidant, 0.05 parts by weight of a fatty acid ester-based lubricant and 0.5 parts by weight of an antistatic agent EA were mixed, and uniform pellets were produced with a 40 mmφ extruder. The same operation as in Example 1 was performed using the obtained pellets, and the physical properties were measured.

 The results are shown in Table-2.

All of the transparency, the antistatic property, and the antistatic property by wiping were good.

Example 14 30% by weight of a block copolymer having a styrene content of 40% by weight, a butadiene content of 10% by weight, and a dimethylpropiolactone (pivalolactone) content of 50% by weight, produced by the method (e) shown below, HI-PS 70% by weight, hindered phenol antioxidant 0.12 parts by weight, phosphorus antioxidant
0.15 parts by weight, 0.05 part by weight of a fatty acid ester-based lubricant and 1.0 part by weight of an antistatic agent EA were mixed to produce uniform pellets at 40 mmφ. Next, Example 1 was performed using the obtained pellets.
The same operation as described above was performed to measure the physical properties. Table 2 shows the results.
It was shown to.

Both the antistatic property and the antistatic property by wiping were good.

(E) Method for producing block copolymer Purified benzene 75 in an autoclave having a capacity of 100
And styrene (4.0 kg) were charged and stirred. Then temperature 30
0.24 mol of n-butyl lithium at 40 ° C. and 30
A minute reaction was carried out to complete the polymerization. Next, butadiene 2.0kg
And the temperature was raised to complete the polymerization. Then styrene 4.
0 kg was charged and the temperature was raised to complete the polymerization. Next, 10.0 kg of pivalolactone was charged and reacted at room temperature for 24 hours to complete the polymerization. Finally, after removing benzene by steam distillation, the polymer slurry was dehydrated and dried.

(Measurement conditions) ・ Haze: Measure the haze of the 2mm part of the three-step plate, in accordance with ASTM D-1003 ・ Surface resistance (blank): In accordance with JIS K-6911 Temperature 23
° C, humidity 60% RH ・ Surface resistance value (after wiping): Measure the surface resistance value after wiping the surface of the molded product 1000 times with a load of 50 g once / second at a temperature of 23. Compliant with JIS K-6911 Temperature 23 ° C, humidity 60% RH ・ Vicat softening point: JIS K-6870 ・ Izod impact value: JIS K-6870 (Effect of the Invention) As shown in the above examples, the permanent antistatic resin composition of the present invention is: It is possible to obtain a resin composition which is excellent in permanent antistatic properties as compared with conventional antistatic resins and does not cause deterioration over time.

Continuation of the front page (56) References JP-A-56-50958 (JP, A) JP-A-58-171434 (JP, A) Patent 2804830 (JP, B2) Patent 2567573 (JP, B2) 37737 (JP, B1) US Patent 3,652,720 (US, A) US Patent 3,695,523 (US, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 53/00-53/02 C08G 63/08 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A block copolymer comprising a polymer block composed of a vinyl aromatic compound, a polymer block composed of a conjugated diene compound and a polymer block composed of a lactone compound, wherein the content of the vinyl aromatic compound is And the weight ratio of the conjugated diene compound content is 10 to 100: 90 to
0, and the sum of the vinyl aromatic compound and the conjugated diene compound is 30 to 59% by weight, and the lactone compound is 70 to 90% by weight.
41% by weight of a block copolymer, a general type styrene resin, a styrene-butadiene graft copolymer resin, a styrene-isoprene-based block copolymer resin,
A permanent antistatic resin composition comprising 100 parts by weight of a resin composition selected from a butadiene-based block copolymer resin and a hydride of the copolymer resin, and 0.1 to 2.0 parts by weight of an antistatic agent. 2. The permanent antistatic resin composition according to claim 1, wherein the lactone compound is a β-ε lactone compound represented by the following general formula. (However, R ₁ , R ₂ and R ₃ are H or an alkyl group of C _{1 to} C ₈ , and n represents an integer of 1 to 5.)