JPH0782458A - Thermoplastic styrene-based resin composition with antistatic properties and its production - Google Patents

Abstract

PURPOSE: To provide the subject compsn. consisting of a polyetheresteramide polymer, a rubber graft polymer and a modified vinyl graft polymer, excellent in mechanical properties and antistatic properties and useful for an optical or magnetic recording medium housing.

CONSTITUTION: An objective compsn. consists of (A) 5-25 wt.% polyetheresteramide polymer represented by the formula (wherein R₁ and R₂ are each H, CH₃ or C₂H₅; PA is a polyamide; PE is a polyalkylene oxide; and n is a constant) containing 10-95 wt.% polyester unit, (B) 60-93 wt.% graft polymer consisting of a rubbery polymer and an aromatic vinyl/vinyl cyanide monomer blend and (C) 2-15 wt.% modified vinyl graft polymer containing 41-90 wt.% copolymer of acrylic ester and/or α,β-unsaturated carboxylic acid anhydride monomer and an olefinic monomer as a main chain and 59-10 wt.% copolymer of an aromatic vinyl monomer and a vinyl cyanide monomer as a branched chain.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a styrene resin composition, and more particularly, to a permanent antistatic charge for constituting an optical or magnetic recording medium housing such as a television, a cassette tape recorder, a video tape recorder and the like. TECHNICAL FIELD The present invention relates to a thermoplastic styrene resin composition having properties and excellent mechanical properties such as impact strength, and a method for producing the same.

[0002]

2. Description of the Related Art A styrene resin composition widely used as a raw material for housings of all electronic products such as televisions, cassette tape recorders, cassette tape players, optical disc jackets, remote control guns, refrigerators and washing machines has been available for a long time. Developed and used. Since such a styrenic resin composition constitutes the appearance of the product, not only the appearance but also the mechanical properties such as impact strength must be good, and electrostatic or electrostatic recording of light or magnetic recording. Dropout
) And it is necessary to maintain permanent antistatic properties to prevent signal, sound or image defects.

As a conventional method for achieving the purpose of such a styrene resin composition, a method of adding a surfactant, conductive carbon black or a metal filler has been used.

Among them, the method of adding conductive carbon or metal filler can obtain the required antistatic property, but it is difficult to color the resin composition and the impact strength is lowered. It was included. In addition, the method of using a surfactant is such that the antistatic function of the resin composition is greatly affected by relative humidity and a stable antistatic effect cannot be obtained. However, there is a problem in that the permanent antistatic property cannot be maintained because it is lost by friction.

A resin composition developed in order to solve such problems is disclosed in Japanese Patent Laid-Open No. 62-116652. This resin composition is mainly composed of a copolymer of polyetheresteramide, a rubber-like graft polymer, and a vinyl-based monomer, and among these, the monomer forming the copolymer is an aromatic compound. Vinyl-based monomers, vinyl cyanide-based monomers, and other vinyl-based monomers copolymerizable therewith were used.

A resin composition similar to the above-mentioned Japanese Unexamined Patent Publication No. 62-116652 is disclosed in Japanese Unexamined Patent Publication No. 62-241945.
And 63-95251. In Japanese Patent Laid-Open Nos. 62-241945 and 63-95251, modified vinyl containing a carboxyl group instead of the copolymer of vinyl monomers in Japanese Patent Laid-Open No. 62-116652 is contained. It is defined as using a polymer, and this modified vinyl polymer is also produced by copolymerizing vinyl monomers.

Further, Japanese Patent Laid-Open No. 1-163252 discloses a polyetheresteramide, a polycarbonate resin,
A modified vinyl resin and a resin composition containing a rubber-like graft polymer as a main component are disclosed. Here, the modified vinyl resin is also an aromatic vinyl monomer, a (meth) acrylic acid ester monomer, It is produced by polymerizing or copolymerizing at least one vinyl monomer selected from vinyl cyanide monomers and maleimide monomers.

[0008]

However, since all of the above cited resin compositions use a modified vinyl resin produced by polymerizing or copolymerizing one or more vinyl monomers, the cost increase due to the polymerization process. It also includes problems such as reduced productivity.

Therefore, in the present invention, a modified vinyl-based graft polymer is used instead of the vinyl-based monomer copolymer which is one of the components of the conventional antistatic styrene-based resin composition. This led to the development of a styrene-based resin composition having a novel composition having good antistatic properties as well as mechanical properties such as impact strength, and a method for producing the same.

The object of the present invention is not to use a linear random polymer obtained by polymerizing a vinyl monomer, but to use a modified vinyl graft polymer graft-polymerized to obtain good mechanical properties and antistatic properties. A styrene-based thermoplastic resin composition having properties is provided.

Another object of the present invention is to provide a method for producing a styrenic thermoplastic resin composition composed of a polyetheresteramide polymer, a rubbery graft polymer, and a vinylic graft polymer. .

[0012]

The thermoplastic styrenic resin composition having an antistatic property of the present invention for achieving the above object is (A) (a1) an amino group having six or more carbon atoms. A salt of a carboxylic acid, a lactam, or a diamine with a dicarboxylic acid having 6 or more carbon atoms, (a2) poly (alkylene oxide) glycol, and (a3) a dicarboxylic acid having 4 to 20 carbon atoms. 5 to 25% by weight of a polyetheresteramide polymer having 10 to 95% by weight of a polyetherester unit, (B) (b1) 10 to 60% by weight of a rubbery polymer, and (b2) an aroma Group vinyl monomer and vinyl cyanide 90 to 40% by weight are copolymerized to obtain a monomer mixture 20 to
95% by weight of graft-polymerized graft polymer 60-
93% by weight, (C) (c1) acrylic acid ester and / or α, β-
Copolymer 41-90% by weight consisting of 5-40% by weight of unsaturated carboxylic acid anhydride monomer and 60-95% by weight of olefinic monomer such as ethylene and propylene, and (c2)
Copolymers 59 to 10 of aromatic vinyl monomer 40 to 90% by weight and vinyl cyanide monomer 60 to 10% by weight
Obtained by graft polymerization of (c1)
A modified vinyl-based graft polymer having a main chain of (c2) as a branched chain and a modified vinyl graft polymer of 2 to 15% by weight is provided.

The present invention also provides a method for producing a styrene-based thermoplastic resin composition composed of a polyetheresteramide polymer, a rubber-like graft polymer, and a modified vinyl-based graph and polymer.

[0014]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific contents of the present invention will be described below with reference to the accompanying drawings.

The thermoplastic styrene resin composition having an antistatic property of the present invention comprises 5 to 25% by weight of (A) a polyetheresteramide polymer and (B) a rubber-like graft polymer 60.
To 93% by weight, and (C) modified graft polymer 2 to 15
It is based on weight%. A detailed description of these components is as follows.

(A) Polyester ester amide polymer This polyether ester amide polymer is a charge-eliminating polymer, which is again (a1) an aminocarboxylic acid having 6 or more carbon atoms, a lactam, or a diamine. With a dicarboxylic acid having three or more carbon atoms, (a2) poly (alkylene oxide) glycol, and (a3) 4-2.
It is composed of a dicarboxylic acid having 0 carbon atoms.

The polyetheresteramide polymer (A) has a structure represented by the following formula.

[0018] In the above formula, R ₁ and R ₂ are H, CH ₃ , or C ₂
H ₅ and PA are polyamides, PE is a polyalkylene oxide, and n is a constant.

The salt (a1) of an aminocarboxylic acid having 6 or more carbon atoms, a lactam, or a dicarboxylic acid and a dicarboxylic acid having 6 or more carbon atoms includes ω-aminocaproic acid, ω-aminoenanthic acid, ω Of aminocarboxylic acids such as aminocapric acid, 1,1-aminoundecanoic acid, 1,2-aminododecanoic acid and the like; lactams such as caprolactam, enantolactam, capryllactam and the like; and hexamethylenediamine-adipic acid There are salts of diamines and dicarboxylic acids such as salts, salts of hexamethylenediamine-isophthalic acid and the like. Desirably a salt of caprolactam, 1,2-aminododecanoic acid, or hexamethyldiamine-adipic acid is used.

The poly (alkylene oxide) glycol (a2) is poly (ethylene oxide) glycol, poly (1,2 and 1,3-propylene oxide) glycol,
Includes poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, block or random copolymers of ethylene oxide and propylene oxide. Desirably poly (ethylene oxide) glycol is used.

The dicarboxylic acid (a3) having 4 to 20 carbon atoms includes terephthalic acid, 1,4-cyclohexacarboxylic acid, sebacic acid, adipic acid, and dodecanocarboxylic acid.

The method for synthesizing the polyetheresteramide polymer (A) is not particularly limited.
PEBAX 4011, which is a static-eliminating polymer which can be used in the methods disclosed in JP-A No. 19 and JP-A-55-133424, and which is already commercially available for such a purpose.
MA 00 (a product of Atochem) may be used.

The unit of this polyether ester is at least 1
It should have a range of 0 to 95% by weight. This is because when the content of the polyether ester amide polymer (A) is 5% by weight or less based on the entire resin composition, the static elimination effect of the resin composition is lowered, and when it is 25% by weight or more, the resin composition This is because the mechanical properties of are deteriorated.

(B) Graft Polymer The graft polymer (B) is a compound added to improve mechanical properties such as impact strength, and is 10 to 60% by weight of the rubbery polymer (b1) and an aromatic compound. Vinyl monomer and vinyl cyanide monomer mixture (b2) 90-40
20 to 95% by weight of the monomer mixture is a polymer obtained by copolymerizing 50% by weight of the monomer mixture. Where 90-40
The aromatic vinyl-based monomer and the vinyl cyanide-based monomer (b2) used in the weight% are 40 to 90% by weight of the aromatic vinyl-based monomer and 60 to 1 of the vinyl cyanide-based monomer.
It is composed of 0% by weight.

The rubbery polymer (b1) used here is a diene rubber such as polybutadiene latex; an acrylic rubber such as polyisoprene latex, polychloroprene latex or polybutyl acrylate latex; and ethylene-propylene-butadiene monomer. There are rubbery polymers that are terpolymers of the terpolymer. Polybutadiene latex is preferably used.

Among the vinyl-based monomers (b2), the aromatic vinyl-based monomers include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, vinyltoluene, monochlorostyrene, dichlorostyrene,
There are dibromostyrene, ethylstyrene, vinylnaphthalene, and divinylbenzene, preferably styrene or α-methylstyrene is used, and vinyl cyanide monomers include acrylonitrile, methacrylonitrile, and ethacrylonitrile, Acrylonitrile is preferably used.

The method for producing the graft polymer (B) from the rubber polymer (b1) and the aromatic vinyl monomer and vinyl monomer (b2) is not particularly limited, and the rubber polymer ( A method in which a mixture of a vinyl-based monomer (b2) and a polymerization initiator are added in the presence of b1) to carry out emulsion graft polymerization can be usually used.

The content of the graft polymer (B) in the resin composition of the present invention is usually maintained at 60 to 93% by weight based on the total resin composition.

(C) Modified Vinyl Graft Polymer The modified vinyl graft polymer (C) used in the present invention is an acrylic ester and / or an α, β-unsaturated carboxylic acid anhydride monomer and an olefin group. Copolymer (c1) 41-90% by weight with monomer, and copolymer (c2) with aromatic vinyl monomer and vinyl cyanide monomer
The polymer is obtained by graft polymerization of 59 to 10% by weight, and is a polymer having (c1) as a main chain and (c2) as a branched chain. The copolymer (c1) is an acrylic acid ester and / or an α, β-unsaturated carboxylic acid anhydride monomer 5 to 4
A copolymer of 0% by weight and 60 to 90% by weight of an olefinic monomer, and acrylic ester monomers usable here include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and vinyl acetate. , Α, β-unsaturated carboxylic acid anhydrides include maleic acid, maleic anhydride, and fumaric acid, and olefinic monomers include ethylene and propylene. The copolymer (c2) is 40 to 90% by weight of an aromatic vinyl monomer and 60 vinyl cyanide monomer.
Aromatic monomers usable herein include styrene, methylstyrene, and halogenated styrene, and vinyl cyanide-based monomers include acrylonitrile.

The modified vinyl-based graft polymer (C)
Should consist of 41-90% by weight of backbone and 59-10% by weight of branched chains. This is because the impact strength is reduced if it is out of this range.

The copolymerization method of each of the copolymer (c1) and the copolymer (c2) and the graft polymerization method of the copolymer (c1) and the copolymer (c2) are carried out by an ordinary polymerization method. Is easily implemented by one of ordinary skill in the art.

The resin composition of the present invention can be used by molding it into a housing of electronic products for optical or magnetic recording media. If necessary, it may be used as a molding material by mixing polybutyl terephthalate (PBT), polyethyl terephthalate (PET), polycarbonate (PC), etc., which are compatible with the resin composition of the present invention, Flame retardancy can also be imparted by adding a halogen-based or phosphorus-based flame retardant.
Further, an antioxidant, a heat stabilizer, a lubricant, a pigment and the like can be appropriately mixed and used.

A transmission electron micrograph of a composition comprising a mixture of the polyetheresteramide polymer (A) and the rubber-like graft polymer (B) is shown in FIG. 1 and shows the polyetheresteramide polymer of the present invention. A transmission electron micrograph of a resin composition comprising a mixture of (A), the rubber-like graft polymer (B), and the modified vinyl-based graft polymer (C) is shown in FIG.

In FIGS. 1 and 2, the large sphere is the graft ABS, and the elongated linear shape in FIG. 1 and the small ellipse in FIG. 2 are assumed to be the polyetheresteramide polymer (A). It is presumed that the change of the elongated linear shape in FIG. 1 to the small elliptical shape in FIG. 2 was caused by the physical or chemical action of the mixed modified vinyl-based graft polymer (C) and the polymer (A). To be done. In other words, it seems that the modified vinyl-based graft polymer (C) improves the compatibility between the polymer (A) and the graft polymer (B). In the resin composition of the present invention, the particles of the polymer (A) are uniformly distributed in the composition as shown in the photograph of FIG.
Has a major axis in the range of ~ 3 μm and a major axis / minor axis ratio of about 1
When it is ~ 6, it has good physical properties.

The following examples are merely one specific example of the present invention, and all simple variations or modifications of the present invention fall within the scope of the present invention, and the protection scope of the present invention is covered by the appended claims. Is specifically limited by

EXAMPLES The examples of the present invention were divided into Examples 1-8 and Comparative Examples 1-5. Examples 1 to 8 are polyetheresteramide polymers (A), which are components of the resin composition of the present invention,
The rubbery graft polymer (B) and the modified vinyl-based graft polymer (C) were changed in kind and content, and Comparative Examples 1 to 5 were prepared by changing one or more of these components. In this example, the components were removed or the content of the modified vinyl-based graft polymer (C) was changed.

First, Examples 1 to 8 and Comparative Examples 1 to 5
A description for each of the components used to carry out is as follows.

(A) Polyester ester amide polymer PEBAX 4011 M manufactured by Atchem
A00 was used as is.

(B) Graft polymer 100 parts by weight of a mixture of polybutadiene latex solid content of 15% by weight, styrene of 62% by weight, and acrylonitrile of 23% by weight, mercaptan of 0.2 parts by weight, potassium persulfate of 0.5 parts by weight, and 0.5 parts by weight of sodium oleate was added and emulsion polymerization was carried out to produce a rubbery graft polymer (B) which is a styrene resin.

(C) Modified Vinyl Graft Polymer As the modified vinyl graft polymer (C) in the present invention, MODIPERI (trademark) A SERIES of NIPPONOIL AND FATS is used, and the present invention is carried out. C used in the example
The ingredients and contents of -1, C-2, C-3, and C-4 are shown in Table 2.

Examples 1-8 Examples 1-8 were prepared by mixing the above-prepared compositions, respectively, as shown in Table 1 below, and L / D = 29 and φ = 4.
Pellet was produced using a 0 mm twin screw extruder (twin screw extruder). The pellets produced were injection-molded to produce impact specimens and 3t × 100 × 100 specimens.

The physical property measuring methods measured in the examples of the present invention and the comparative examples are as follows.

Izod impact strength Measured according to ASTM D648 (1/8 〓 notch 23 ° C.).

Surface Resistivity Based on ASTM D257, surface resistance was measured immediately after injecting pellets, and at a temperature of 23 ° C. and 50 ° C.
After 200 days under relative humidity of 20%, the cloth was washed with 20% of ethanol for 5 times, stored again at a temperature of 23 ° C. and relative humidity of 50% for 48 hours, and then measured.

Half-life Injection specimens were stored at a temperature of 23 ° C. and a relative humidity of 50% for 480 hours and then stored in STATICHONESMETER (product of SHISHIDO ELECTRIC, Type S-5109).
) Was used under the conditions of an applied voltage of 8000 V, a distance between the applied voltage and the sample of 10 mm, an application time of 60 seconds, and a distance of 5 mm between the detection electrode and the sample.

Surface Appearance Judgment After injecting a 3t × 100 × 100 test piece, the surface was visually inspected.

(Legend: ☆ Excellent, ○ Excellent, × Poor)

[0048]

[Table 1]

Note) *: Surface resistivity immediately after injection **: Surface resistivity 200 days after injection Comparative Examples 1 to 5 Comparative Examples 1 to 5 are as shown in Table 3 below. The above-prepared compositions were mixed, and the same method as in Examples 1 to 8 was performed.

[0050]

[Table 2]

Note) g: Graft bond

[0052]

[Table 3]

Note) * EVA: ethylene vinyl acetate (vinyl acetate content = 20%) ** NO-BK: NO BREAK ***: surface resistivity immediately after injection ****: surface after 200 days from injection Resistivity

[0054]

As described above, according to the present invention,
By using the vinyl-based graft polymer, it is possible to provide a styrene-based resin composition having a composition excellent in not only mechanical properties but also antistatic properties and a method for producing the same.

[Brief description of drawings]

FIG. 1 is a transmission electron micrograph of a mixture of a polyetheresteramide polymer and a rubber-like graft polymer.

FIG. 2 is a transmission electron micrograph of a styrene resin composition which is a mixture of the polyetheresteramide polymer of the present invention, a rubber graft polymer, and a modified vinyl graft polymer.

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[Procedure amendment]

[Submission date] September 8, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Change

[Correction content]

[Brief description of drawings]

FIG. 1 is a transmission electron micrograph of a mixture (particle structure) of a polyetheresteramide polymer and a rubber-like graft polymer.

FIG. 2 is a transmission electron micrograph of a styrene resin composition (particle structure) , which is a mixture of the polyetheresteramide polymer of the present invention, a rubber-like graft polymer, and a modified vinyl-based graft polymer. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 30, 1993

[Procedure Amendment 1]

[Document name to be corrected] Drawing

[Correction target item name] All drawings

[Correction method] Change

[Correction content]

[Figure 1]

[Fig. 2]

Claims (10)

[Claims] 1. (A) (a1) A salt of an aminocarboxylic acid having 6 or more carbon atoms, a lactam, or a diamine and a dicarboxylic acid having 6 or more carbon atoms, (a)
2) poly (alkylene oxide) glycol, and (a
3) a dicarboxylic acid having 4 to 20 carbon atoms, wherein the unit of the polyetherester is 10 to 95% by weight, and 5 to 25% by weight of a polyetheresteramide polymer having the following structural formula, (In the above formula, R ₁ and R ₂ are H, CH ₃ , or C
₂ H ₅ , PA is polyamide, PE is polyalkylene oxide, and n is a constant. ) (B) (b1) 10 to 60 wt% of a rubbery polymer, and (b2) 90 to 40 wt% of an aromatic vinyl-based monomer and a vinyl cyanide-based copolymer are copolymerized to prepare a monomer mixture 20 to
95% by weight of graft-polymerized graft polymer 60-
93% by weight, (C) (c1) acrylic acid ester and / or α, β-
Copolymer 41-90% by weight consisting of 5-40% by weight of unsaturated carboxylic acid anhydride monomer and 60-95% by weight of olefinic monomer such as ethylene and propylene, and (c2)
Copolymers 59 to 10 of aromatic vinyl monomer 40 to 90% by weight and vinyl cyanide monomer 60 to 10% by weight
Obtained by graft polymerization of (c1)
A thermoplastic styrene resin composition having an antistatic property, characterized by comprising 2 to 15% by weight of a modified vinyl-based graft polymer having a main chain of (c2) as a branched chain. 2. A group in which the rubbery polymer (b1) of the graft polymer (B) comprises a diene rubber, an acrylic rubber, and a rubber of a terpolymer of an ethylene-propylene-diene monomer. The thermoplastic styrene resin composition having an antistatic property according to claim 1, which is one selected from the group consisting of: 3. The aromatic vinyl-based monomer of the graft polymer (B) is styrene, t-butylstyrene, alphamethylstyrene, p-methylstyrene, vinyltoluene, monochlorostyrene, dichlorostyrene, dibromostyrene, The thermoplastic styrene resin composition having an antistatic property according to claim 2, which is one selected from the group consisting of ethylstyrene, vinylnaphthalene, and divinylbenzene. 4. The vinyl cyanide-based monomer of the graft polymer (B) is one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile. 3. A thermoplastic styrene resin composition having an antistatic property as described in 3. 5. The antistatic property according to claim 1, wherein the acrylic acid ester monomer is one selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, and vinyl acetate. A thermoplastic styrene resin composition having. 6. The α, β-unsaturated carboxylic acid anhydride is one selected from the group consisting of maleic acid, maleic anhydride, and fumaric acid.
A thermoplastic styrene-based resin composition having the above-mentioned antistatic property. 7. The thermoplastic styrene resin composition having an antistatic property according to claim 6, wherein the olefinic monomer is ethylene or propylene. 8. The antistatic heat according to claim 7, wherein the aromatic vinyl-based monomer is one selected from the group consisting of styrene, methylstyrene, and halogenated styrene. Plastic styrene resin composition. 9. The thermoplastic styrene resin composition having an antistatic property according to claim 8, wherein the vinyl cyanide monomer is acrylonitrile. (A) (a1) A salt of an aminocarboxylic acid having 6 or more carbon atoms, a lactam, or a diamine and a dicarboxylic acid having 6 or more carbon atoms, (a)
2) poly (alkylene oxide) glycol, and (a
3) a dicarboxylic acid having 4 to 20 carbon atoms, wherein the unit of the polyetherester is 10 to 95% by weight, and 5 to 40% by weight of a polyetheresteramide polymer having the following structural formula, (In the above formula, R ₁ and R ₂ are H, CH ₃ , or C
₂ H ₅ , PA is polyamide, PE is polyalkylene oxide, and n is a constant. ) (B) (b1) 10 to 60% by weight of a rubbery polymer, and (b2) 90 to 40% by weight of an aromatic vinyl-based monomer and a vinyl cyanide-based monomer are copolymerized to obtain a monomer mixture 20 to
95% by weight of graft-polymerized graft polymer 20 to
90% by weight, (C) (c1) acrylic acid ester and / or α, β-
Copolymer 41-90% by weight consisting of 5-40% by weight of unsaturated carboxylic acid anhydride monomer and 60-95% by weight of olefinic monomer such as ethylene and propylene, and (c2)
Copolymers 59 to 10 of aromatic vinyl monomer 40 to 90% by weight and vinyl cyanide monomer 60 to 10% by weight
Obtained by graft polymerization of (c1)
A modified vinyl-based graft polymer having 2 to 15% by weight of (c2) as a branched chain and (c2) as a branched chain, is mixed with a mixer to produce pellets through an extruder. A method for producing a thermoplastic resin composition.