JPH0270739A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having good mechanical properties, moldability, permanent antistatic properties and molding heat stability by mixing a rubber-modified styrene polymer containing a hydroxylated vinyl monomer as a comonomer with a polyamide elastomer. CONSTITUTION:The production of a thermoplastic resin composition by mixing 10-99wt.% rubber-modified styrene thermoplastic resin (A) comprising a rubber- modified styrene polymer and a styrene polymer at least one of which contains a hydroxylated vinyl monomer (e.g., 2-hydroxyethyl methacrylate) as a comonomer component with 90-1wt.% polyamide elastomer is conducted in such a manner that 0.01-15wt.% said hydroxylated vinyl monomer may be contained in the composition as a comonomer component. A thermoplastic resin composition having excellent molding stability and moldability and permanent antistatic properties can be obtained.

Description

[Detailed description of the invention] [Industrial application field] The present invention provides mechanical properties, moldability, permanent antistatic properties,
The present invention relates to a thermoplastic resin composition having molding heat stability.

[Conventional technology]

Synthetic polymer materials are used in a wide range of fields due to their excellent properties, but they generally have high electrical resistivity and are easily charged, resulting in various problems caused by static electricity.

Conventionally, for the purpose of imparting antistatic properties to synthetic polymer materials, there have been methods for incorporating water-absorbing compounds such as polyalkylene oxide and antistatic agents into synthetic polymers, and ■ adding surfactants to synthetic polymers. A commonly used method is to apply it to the surface of molecules. However, sufficient antistatic performance has not been achieved by any of these methods, and when washing with water or wiping the surface, the antistatic performance disappears or the components mixed in are bleed out, resulting in a loss of quality as a material. There are problems such as a decrease in antistatic properties and a decrease in antistatic properties over time.

On the other hand, so-called polyether ester amide, in which polyamide and polyester are ester bonded via dicarboxylic acid, is known to have excellent rubber elasticity and good antistatic properties. However, polyether ester amide has rubber elasticity and insufficient mechanical strength, so it is required to have rigidity and toughness, and has the drawback that it is not sufficient as a structural material. Moreover, polyether ester amide can be used with other thermoplastic resins such as polystyrene, styrene-acrylonitrile copolymer (A
s resin), polymethyl methacrylate, styrene-methyl methacrylate copolymer, and acrylonitrile-butadiene-styrene terpolymer (ABS resin). Therefore, for example, in JP-A-61-246244 (hereinafter referred to as "prior art 1"), (A) polyether ester amide, (B) rubbery polymer, (meth)acrylic ester and/or aromatic Graft copolymers obtained by polymerizing monomers such as vinyl, and copolymers obtained by copolymerizing monomer mixtures such as (c) (meth)acrylic acid ester, aromatic vinyl, and/or vinyl cyanide. (Styrenic polymer)
It is disclosed that a composition consisting of the following has permanent antistatic properties.

However, the composition of Prior Art 1 does not have sufficient mechanical strength such as impact strength because the compatibility between the polyether ester amide and the styrene polymer is still poor.
It cannot be put to practical use.

Furthermore, JP-A No. 60-23435 (hereinafter referred to as "prior art 2") discloses blending a modified vinyl polymer containing a carboxyl group with polyether ester amide; Although the mechanical strength of the composition is improved, it has the disadvantage of exhibiting poor appearance such as silver streaks and matteness due to the self-crosslinking reaction of carboxyl groups. Moreover, in this prior art 2, if the resin is retained during molding, the mechanical strength will be reduced as well as the aforementioned poor appearance, and the thermal stability will be poor.

[Problem to be solved by the invention]

The present invention was made against the background of the problems of the prior art, and aims to provide a thermoplastic resin composition that has excellent molding thermal stability and molding processability, and has excellent permanent antistatic properties. do.

[Means to solve the problem]

The present invention comprises (a) a rubber-modified styrenic polymer or a rubber-modified styrenic polymer and a styrene-based polymer, and a small amount of the polymer (one of which contains a hydroxyl group-containing vinyl monomer as a copolymerization component). rubber-modified styrenic thermoplastic resin (hereinafter sometimes referred to as "component (A)") 10-99
weight% and (b) polyamide elastomer (hereinafter referred to as “(b)
) 90 to 1% by weight (sometimes referred to as “component”)
(a) + (b) = 100% by weight], the composition containing 0.01 to 15% by weight of the hydroxyl group-containing vinyl monomer as a copolymerization component. The present invention provides a thermoplastic resin composition characterized by the following.

The (a) rubber-modified styrenic thermoplastic resin used in the composition of the present invention includes: (i) rubber-modified styrenic polymer;
or■ It is a mixture of rubber-modified styrenic polymer and styrenic polymer (not rubber-modified), in which the rubbery polymer is mixed into a specific styrenic polymer for the purpose of obtaining a high degree of impact resistance. This is what I did. As this mixing method,
(Although a simple mechanical blending method may be used, in order to obtain good compatibility, a so-called graft copolymerization method, in which a styrene monomer or the like is graft copolymerized in the presence of a rubbery polymer, is recommended.) The obtained product is more preferable.Also, the so-called graft-blend method, in which the rubber-modified styrenic polymer (graft copolymer) obtained by this method is mixed with a styrenic polymer obtained by a separate method. It is also preferable to use one obtained by.

Here, the types of rubbery polymers used include polybutadiene, diene rubber such as styrene-butadiene copolymer, acrylic copolymer, ethylene-propylene-(diene) copolymer, chlorinated Examples include polyethylene and polyurethane, among which polybutadiene is preferably used.

As for the method of copolymerizing a hydroxyl group-containing vinyl monomer with (a) rubber-modified styrenic pre-desirable resin used in the present invention, the thermoplastic resin may be (i) rubber-modified styrenic polymer, or (i) rubber-modified styrene Since it is made of a mixture of a rubber-modified styrene-based polymer and a styrene-based polymer, the rubber-modified styrene-based polymer contains a hydroxyl group-containing vinyl monomer as a copolymer component. (2) In the case of a mixture, at least one of the polymers contains a hydroxyl group-containing vinyl monomer as a copolymerization component of a styrene monomer.

Examples of the styrene monomer include styrene, α-methylstyrene, and bromostyrene, among which styrene is most suitable.

Further, the hydroxyl group-containing vinyl monomer is a compound having at least one unsaturated bond (double bond, triple bond) and containing a hydroxyl group. Typical examples include alcohols with double bonds, alcohols with triple bonds, esters of -valent or divalent unsaturated carboxylic acids and unsubstituted dihydric alcohols, and unsubstituted trivalent alcohols of unsaturated carboxylic acids. Examples include esters with hydrohydric alcohols, esters with unsubstituted tetrahydric alcohols, and esters with unsubstituted trihydric or higher alcohols.

Among the hydroxyl group-containing vinyl monomers used in the present invention, preferred representative examples include 3-hydroxy-1-propane, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans- 4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene, cis-5-hydroxy-2-pentene, trans-5-hydroxy-2-pentene, cis-1,4-dihydroxy-2- Butene, trans-1,4-dihydroxy-2-
Butene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl crotonate, 2,3,4,5
．． 6-pentahydroxyhexyl acrylate, 2,3
, 4,5°6-pentahydroxyhexyl methacrylate, 2.3.4.5-tetrahydroxypentyl acrylate, 2,3,4.5-tetrahydroxypentyl methacrylate, and the like.

Among these, it is preferable to use 2-hydroxyethyl methacrylate.

These hydroxyl group-containing vinyl monomers can be used alone or in combination of two or more.

The content of the hydroxyl group-containing vinyl monomer is 0.01 to 15 weight percent, by weight, in the total composition containing (a) the rubber-modified styrenic thermoplastic resin and (b) the polyamide elastomer described below. o, i - 5% by weight, more preferably 0.1 - 2% by weight, particularly preferably 0.1% by weight or more and less than 0.5% by weight. When the amount of vinyl monomer used in the total composition is less than 0.01% by weight, (
b) Compatibility with the polyamide elastomer decreases, resulting in a decrease in impact resistance and antistatic properties, which is undesirable.On the other hand, if it exceeds 15% by weight, molding thermal stability and molding processability decrease. Undesirable. In particular, the content of the hydroxyl group-containing vinyl monomer in the entire composition is from O,1 to
2% by weight, preferably 0.1% by weight or more, 0.5% by weight
If it is less than 100%, a composition with an even better balance of physical properties among molding heat stability, molding processability, antistatic property, and impact resistance can be obtained.

Furthermore, if necessary, it is also possible to carry out copolymerization using monomers other than the hydroxyl group-containing vinyl monomers that can be copolymerized with these styrene monomers. Such other monomers include acrylonitrile, methacrylonitrile, methyl methacrylate, N-phenylmaleimide, N
-Cyclohexylmaleimide and the like.

(a) In the rubber-modified styrenic thermoplastic resin, when a styrene monomer is used alone, it is difficult to develop impact resistance, so it is preferable to copolymerize acrylonitrile.

(a) When graft copolymerizing a hydroxyl group-containing vinyl monomer to a rubber-modified styrene thermoplastic resin, the base materials include: ■ a rubbery polymer, ■ a graft layer of a graft copolymer,
Alternatively, (2) non-grafted styrene polymers may be mentioned, but among these, (2) or (2), particularly (2) is preferable.

Specifically, the rubber-modified styrenic thermoplastic resin (a) obtained in this way is a conventional acrylonitrile-
Butadiene-styrene resin (A BS resin), acrylonitrile-ethylene propylene-styrene resin (AE
S resin), methyl methacrylate-butadiene styrene resin (MBS resin), acrylonitrile-butadiene-
Copolymers such as methyl methacrylate-styrene resin, acrylonitrile-n-butyl acrylate-styrene resin (AAS resin), rubber-modified polystyrene (high-impact polystyrene; HIPS), and heat-resistant rubber-modified styrenic resin using α-methylstyrene. When producing a resin, by polymerizing a part of the monomer in the copolymer resin or the styrenic polymer mixed in the copolymer resin with a hydroxyl group-containing vinyl monomer, hydroxyl groups can be removed. It contains a vinyl monomer.

Among these (a) rubber-modified styrenic thermoplastic resins, those prepared by copolymerizing and containing a hydroxyl group-containing vinyl monomer in a conventional ABS resin are most suitable.

(a) The rubber-modified styrenic thermoplastic resin used in the present invention is produced by emulsion polymerization, solution polymerization, suspension polymerization, or the like.

Further, at this time, as the polymerization initiator, molecular weight regulator, emulsifier, dispersant, solvent, etc. used in the polymerization, those normally used in these polymerization methods can be used as they are.

(a) As a preferred method for producing a rubber-modified styrenic thermoplastic resin, in the presence of a rubbery polymer obtained by emulsion polymerization, a monomer, an additional emulsifier, a monomer,
Using a polymerization initiator, the polymerization temperature is generally 30 to 150°C1
Polymerization time 1 to 15 hours, polymerization pressure car 1.0 to 5.0 kg
By mixing a graft copolymer obtained by graft copolymerization under the conditions of /d (including ungrafted styrenic polymer) and a styrenic polymer obtained by emulsion polymerization or solution polymerization. Manufacture.

Next, as the polyamide elastomer used in the present invention, aminocarboxylic acids or lactams having carbon numbers as hard segments of m+1 or more and 12
The nylon mn salt (X) of is 20 to 90% by weight, more preferably 80 to 90% by weight.

(b) If the proportion of component X in the elastomer is less than 10% by weight, the compatibility with component (a) will be poor, while if it exceeds 95% by weight, the antistatic properties will be poor, which is not preferred.

The aminocarboxylic acid or lactam having 6 or more carbon atoms or the nylon mn salt (X) with m+n≧12 is,
Aminocarboxylic acids such as ω-aminocaproic acid, ω-aminoenanoic acid, ω-aminocaprylic acid, ω-aminobergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid; caprolactam, laurolactam, etc. Lactams; nylon 6.6, nylon 6.10, nylon 6.12, nylon 11°6, nylon 11,10, nylon 12,6, nylon 11,
Examples include nylon salts such as 12, nylon 12,6, nylon 12.10, and nylon 12.12.

In addition, poly(alkylene oxide) glycol (Y) includes polyethylene glycol, poly(1,2 and 1.3-propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, ethylene oxide and Examples include block or random copolymers with propylene oxide, block or random copolymers with ethylene oxide and tetrahydrofuran, and the like.

The number average molecular weight of these glycols (Y) is 200
-6,000, preferably 250-4,000.

Among these glycols (Y), polyethylene glycol is particularly preferably used because of its excellent antistatic properties.

In addition, in the present invention, both ends of poly(alkylene oxide) glycol (Y) may be aminated or carboxylated.

The bond between component (X) and component (Y) may be an ester bond or an amide bond, depending on the terminal group of the polyamide elastomer (b).

During this bonding, a third component such as dicarboxylic acid or diamine can be used.

The dicarboxylic acid has 4 to 20 carbon atoms, such as terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, and naphthalene-2,7-dicarboxylic acid.
-dicarboxylic acid, diphenyl-4,4-dicarboxylic acid,
Aromatic dicarboxylic acids such as diphenoxyethanedicarboxylic acid and sodium 3-sulfoisophthalate; alicyclic acids such as 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and dicyclohexyl-4,4-dicarboxylic acid; dicarboxylic acids and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, and mixtures thereof, in particular terephthalic acid, isophthalic acid, 1.4-
Cyclohexanedicarboxylic acid, sebacic acid, adipic acid, and dodecanedicarboxylic acid are preferably used from the viewpoint of polymerizability, color tone, and physical properties.

Further, as the diamine, aromatic, alicyclic, and aliphatic diamines are used. Specifically, the aliphatic diamine includes hexamethylene diamine.

(b) The method for synthesizing the polyamide elastomer is not particularly limited, but methods disclosed in Japanese Patent Publication No. 56-45419, Japanese Patent Application Laid-Open No. 55-133424, etc. can be employed, for example.

In addition, (b) as the polyamide elastomer, (a) an amine carboxylic acid or lactam having 6 or more carbon atoms, or a salt of a diamine and dicarboxylic acid having 6 or more carbon atoms, (b)
A polyether ester amide composed of polyethylene glycol having a number average molecular weight of 200 to 6,000 and (c) a dicarboxylic acid having 4 to 20 carbon atoms, the polyether ester having a polyether ester unit content of 10 to 95% by weight. When an amide is used, a thermoplastic resin composition having much better antistatic properties can be obtained.

Among these, preferred as component (a) are caprolactam, 12-aminododecanoic acid, and hexamethylenediamine adipate.

In addition, as component (b), the number average molecular weight is 200 to 6.
,000, preferably 250 to 4,000, and when the number average molecular weight is within this range, products with excellent mechanical properties and antistatic properties can be obtained.

Further, as the dicarboxylic acid of component (c), terephthalic acid, isophthalic acid, l,4-cyclohexanedicarboxylic acid, sebacic acid, adipic acid, and dodecanoic acid can be mentioned, and when these dicarboxylic acids are used, polymerizable ,
Excellent color tone.

Furthermore, when the polyether ester unit content in the polyether ester amide is 10 to 95% by weight, a composition with even better mechanical properties and antistatic properties can be obtained.

The thermoplastic resin composition of the present invention has the above-mentioned (a) rubber-modified styrenic thermoplastic resin and (b) a polyamide elastomer as main components, and the blending ratio of both is such that the (i) component is 10 to 99% by weight. %, preferably 40 to 95% by weight, more preferably 60 to 93% by weight, component (b) is 90 to 1
0% by weight, preferably 60 to 5% by weight, more preferably 40 to 7% by weight [however, (a) + (b) = 100% by weight], and if the polyamide elastomer (b) is less than 1% by weight, molding Processability, antistatic properties, and impact strength are insufficient, while if it exceeds 90% by weight, the composition becomes flexible and has poor mechanical properties, which is not preferable.

The thermoplastic resin composition of the present invention comprises the component (a) and (b).
) components using a conventional mixing method. For example, after mixing each component in a mixer, they are melt-kneaded and granulated in an extruder at 200 to 280"C. Furthermore, it is easier to melt and knead each component directly in a molding machine and mold it. Can be done.

The composition of the present invention has the above-mentioned components (a) and (b) as main components, but in addition to the resin composition of the present invention, other thermoplastic polymers such as vinyl chloride resin and polyolefin may be added. It can contain about 50 weight or less of various ordinary synthetic resins such as resin, polyamide, polybutylene terephthalate, polyethylene terephthalate, polycarbonate, polyphenylene ether, polyglutarimide, styrene-butadiene block copolymer, or elastomer. .

Moreover, various compounding agents can be added to the composition of the present invention.

These compounding agents include, for example, 2,6-di-t-butyl-4-methylphenol, 2-(1methylcyclohexyl)-4,6-dimethylphenol, 2,2-methylene-bis-(4-ethyl -6-mu-butylphenol)
, 4.4'-thiobis-(6-t-butyl-3-methylphenol), dilaurylthiodipropionate, tris(di-nonylphenyl)phosphite, wax, and other antioxidants; p-t-butyl phenyl salicylate,
UV absorbers such as 2,2'-dihydroxy-4-methoxybenzophenone, 2-(2'-hydroxy-4'-n-octoxyphenyl)benzotriazole; paraffin wax, stearic acid, hydrogenated oil, stearamide , methylene bisstearamide, n-butyl stearate, ketone wax, octyl alcohol, lauryl alcohol, hydroxystearic acid triglyceride, and other lubricants; antimony oxide, ammonium hydroxide, zinc borate, tricresyl phosphate, tris(dichloropropyl) )Flame retardants such as phosphates, chlorinated paraffins, tetrabromobutane, hexabromobenzene, and tetrabromobisphenol A; antistatic agents such as stearamidopropyldimethyl-β-hydroxyethylammonium nitrate; titanium oxide, carbon black, etc. Colorants; fillers such as calcium carbonate, clay, silica, glass fibers, glass spheres, and carbon fibers; pigments; and the like.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples. In the examples, parts and percentages are based on weight unless otherwise specified.

Reference Example 1 (Rubber modified styrenic polymer G-1, G-2
) In a glass flask equipped with a stirrer and having an internal volume of 7.
After adding the chemical solution with the batch composition shown in the table and replacing the air inside the flask with nitrogen gas, the jacket was
The temperature inside the flask was raised to 40''C while controlling the temperature at °C.

Next, in a flask were dissolved 10 parts of water, 0.3 parts of sodium birophosphate, 0.35 parts of dextrose, 0.01 parts of ferrous sulfate, and 0 parts of cumene hydroperoxide.
．． 1 part was added to initiate the polymerization reaction.

One hour after the start of the reaction, the chemical solution of the increment mixture shown in Table 1 was continuously added over a period of three hours, and the reaction was continued for another hour, and the reaction was almost completed.

To the obtained graft copolymer (rubber-modified styrenic polymer) latex, 1.0 part of 2°6-t-butyl para-cresol was added as an anti-aging agent, and then sulfuric acid (2 parts per 100 minutes of polymer) was added. ) was added and solidified at 90°C.

Next, this was separated, washed with water, dehydrated, and dried to obtain rubber-modified styrenic polymers G-1 and G-2.

(Margins below) Table 1 *l) Manufactured by Nippon Synthetic Rubber ■, #0700 *2) Manufactured by Nippon Synthetic Rubber ■, #0561 Reference Example 2 (Production of styrenic polymers M-1 to M-7) Stirrer A second glass flask with an internal volume of 71
After adding the chemical solution shown in the table and replacing the air inside the flask with nitrogen gas, the temperature inside the flask was raised to 50°C while controlling the jacket at 70°C.

Next, 0.3 parts of potassium persulfate dissolved in 4 parts of water and 0.1 parts of sodium sulfite dissolved in 1 part of water were added to the flask.
1 part was added thereto, and a copolymerization reaction was carried out for 3 hours.

Calcium chloride (2 parts per 100 minutes of polymer) was added to the obtained styrenic polymer latex and coagulated at 90"C. This was then separated, washed with water, dehydrated, and dried. Styrenic polymers M-1 to M shown in Table 2
-7 was obtained.

Reference Example 3 (Manufacture of Rubber Modified Styrenic Polymer G-3) After purging the inside of a stainless steel reactor with an internal volume of 652 and equipped with a paddle type stirrer with nitrogen gas, the iodine value was 15, the Mooney viscosity was 65, and the propylene content was 43% and containing ethylidene norbornene as a diene component (manufactured by Japan Synthetic Rubber ■, JSREP24), 24 parts of EPDM, 56 parts of styrene, 20 parts of acrylonitrile, and 100 parts of toluene were heated at 50°C until the rubber was completely dissolved. Stir and
Next, 0.1 part of 1-dodecyl mercaptan, 0.2 part of dibenzoyl peroxide, 1-butylperoxy-1
- After adding 0.2 part of propyl carbonate and 0.1 part of dicumyl peroxide, the temperature was raised to 80°C for 3 hours, then to 100°C for 3 hours, and then to 125°C. The temperature was raised and the polymerization reaction was carried out for 3 hours, for a total of 6 hours.

After removing unreacted monomers and solvent by steam distillation, the mixture was crushed and dried to obtain a polymer.

Examples 1 to 12, Comparative Examples 1 to 9 (a) Rubber modified styrenic polymers G-1 to G-2 obtained in Reference Example 1 and styrene obtained in Reference Example 2 as rubber-modified styrenic resins system polymers M-1 to M-7, rubber-modified styrenic polymer G-3 obtained in Reference Example 3, styrene-acrylonitrile copolymer resin (AS resin, manufactured by Nippon Synthetic Rubber ■, AS-240, Contains 124.5% bound acrylonitrile, methyl ethyl ketone 30'C [η]
=0.60), (B) as polyamide elastomer,
PAE-A (manufactured by ATOCHEM, PEBAX401
1. Polyether component; polyethylene glycol),
PAE-B (manufactured by ATOCHEM, PEBAX553
3. Polyether component; tetramethylene glycol):
PA-A (manufactured by Allied, Capron 8200i Nylon 6) was mixed using a Henschel mixer at the mixing ratio shown in Table 3.

Further, 50 parts of the mixture was granulated at a temperature of 230°C using a twin-screw vented extruder, dried at 90°C, and then injection molded at 230°C. Various physical properties shown in were measured.

The Izot impact strength and gloss thermal stability evaluation test pieces were molded using an injection molding machine at a molding temperature of 2.
A test piece for Izotsu impact strength and gloss measurement was molded in a 21-minute cycle at 30°C, and then the molding material was put into the cylinder and left in that state for 10 minutes (retention).
After that, it was molded in a 1-minute cycle to obtain a retained test piece.

In addition, the method of molding the thermal stability evaluation test piece for antistatic property (antistatic property) was to use an injection molding machine with a molding cycle of 1 minute.
A disk having a diameter of 100 nna and a thickness of 2III m was molded at a molding temperature of 230''C and 1270°C.

Evaluation of various physical properties measured using the above test pieces was performed by the methods shown below.

Melt flow rate is ASTM D1238 (24
Measured at 0°C).

The heating deformation temperature is ASTM D648 (load 18
, 6 kg/cd, without annealing).

Izod impact strength was measured using ASTM D256 (notched).

Glossiness was measured according to ASTM D523 (three scale thickness).

The antistatic properties were determined by conditioning the disks molded at 230°C1 or 270'C in a relative humidity of 50% and an ambient temperature of 23°C for 24 hours after molding was completed. The surface resistivity of the test piece was measured using a 4329 super insulation resistance meter. In addition, using a test piece molded at 230°C, the relative humidity was 5.
After being left for one month at 0% and an environmental temperature of 23°C, it was washed with a detergent to remove surface moisture, conditioned again for 24 hours under the above conditions, and the surface resistivity was measured in the same manner.

As is clear from Table 3, Examples 1 to 11 are thermoplastic resin compositions of the present invention, and the objectives of the present invention are thermal stability, mechanical properties, moldability, and antistatic properties during molding. It turns out that he has excellent sex.

On the other hand, Comparative Example 1 is a thermoplastic resin composition that does not use (b) polyamide elastomer, which is outside the scope of the present invention, and is inferior in antistatic properties and moldability. Comparative Example 2 is an example in which a rubber-modified styrene thermoplastic resin containing no hydroxyl group-containing vinyl monomer was used, and the impact resistance was poor.

Comparative Example 3 is an example in which the content of the hydroxyl group-containing vinyl monomer exceeds the range of the present invention, and is inferior in thermal stability and moldability.

Comparative Example 4 is an example in which the amount of rubber-modified styrenic thermoplastic resin exceeds the scope of the present invention, and is inferior in moldability and antistatic properties.

Comparative Example 5 is an example in which the rubber-modified styrenic thermoplastic resin is less than the range of the present invention, and is rubber-like and not a resin. Comparative Example 6 is an example in which a carboxyl group-containing vinyl monomer was used instead of a hydroxyl group-containing vinyl monomer, and the thermal stability was poor.

Comparative Example 7 is an example in which acrylamide was used in place of the hydroxyl group-containing vinyl monomer, and the thermal stability was poor. Comparative example 8~
No. 9 is an example in which polyamide resin (nylon) was used instead of polyamide elastomer, and the antistatic property was poor.

[Effects of the Invention] The present invention provides a thermoplastic resin composition consisting of a rubber-modified styrenic thermoplastic resin copolymerized with a specific amount of a hydroxyl group-containing vinyl monomer and a polyamide elastomer. Or impact resistance even when molded at high temperatures.
Because it has extremely excellent thermal stability with little reduction in gloss and antistatic properties, there is little change in quality even when molded under harsh molding conditions due to diversification of applications in recent years, and therefore it has become extremely popular in industry. It is a useful thermoplastic resin composition.

Patent applicant: Japan Synthetic Rubber Co., Ltd. Agent: Patent attorney Takashi Shirai Procedural amendment (spontaneous) August 9, 1999

Claims (2)

[Claims] (1) (A) Rubber modified consisting of a rubber modified styrenic polymer or a rubber modified styrenic polymer and a styrene polymer, and at least one of the polymers contains a hydroxyl group-containing vinyl monomer as a copolymerization component. Styrenic thermoplastic resin 1
0 to 99% by weight and (b) polyamide elastomer 90
~1% by weight [However, (a) + (b) = 100% by weight]
1. A thermoplastic resin composition comprising 0.01 to 15% by weight of the hydroxyl group-containing vinyl monomer as a copolymerization component. (2) (b) The polyamide elastomer is (a) an amine carboxylic acid or lactam having 6 or more carbon atoms, or a salt of a diamine and dicarboxylic acid having 6 or more carbon atoms, (b) a number average molecular weight of 200 to 6,000. 2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is a polyether ester amide composed of polyethylene glycol and (c) a dicarboxylic acid having 4 to 20 carbon atoms, and the polyether ester unit content is 10 to 95% by weight.