JPH0813919B2 - Thermoplastic resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a flexible thermoplastic resin composition having excellent heat resistance, impact resistance, molding processability, chemical resistance, and antistatic property.

b. Conventional technology A rubber-reinforced styrene resin is a polybutadiene rubber made by graft-copolymerizing styrene and acrylonitrile.
As represented by S resin, it is used in many fields today, but flexible materials are demanded with the diversification of application fields, and modification is attempted by increasing the amount of rubbery polymer and blending elastomers. Has been. However, with these methods, heat resistance, molding processability, and paintability are significantly reduced, although they are flexible. Therefore, at present, it is not always possible to satisfy the performance required in the field requiring heat resistance such as automobile parts.

As a method for improving this, it is disclosed in Japanese Patent Application No. 61-100047 that a polyamide elastomer is blended with a rubber-reinforced styrene resin, but it is a field requiring heat resistance and impact resistance of automobile parts and the like. Then, the impact resistance was not always satisfactory.

On the other hand, maleimide resins are resins with excellent heat resistance and are used as automobile parts and parts for electric and electronic equipment, but they are not always satisfactory in impact resistance, molding processability and chemical resistance. It was

Further, when the rubber-reinforced styrene-based resin and the maleimide-based resin are used as parts for electric / electronic devices, their antistatic property becomes a problem. That is, if electric charges are applied to the parts molded from these resins, the electric charges may adversely affect the performance of electric / electronic devices.

In addition, products molded using resin with low antistatic properties are
Dust tends to adhere to the product, resulting in defective external fitting, which significantly reduces the commercial value.

c. Problems to be Solved by the Invention As described above, according to the conventional method, although it was possible to obtain a flexible resin having good heat resistance and good moldability, impact resistance and antistatic property were obtained. It was not possible to obtain a combined resin.

Therefore, as a result of intensive studies, the present inventors have found that a composition comprising a styrene-based copolymer resin obtained by copolymerizing a hydroxyl group-containing unsaturated compound and a polyamide-based elastomer has heat resistance, impact resistance, molding processability, and resistance to molding. The inventors have found that they have excellent chemical properties and antistatic properties, and have reached the present invention.

d. Means for Solving Problems That is, the present invention provides (a) 5 to 99% by weight of a styrene copolymer resin copolymerized with a hydroxyl group-containing unsaturated compound, and (b) a polyamide elastomer 1 to 95. The present invention provides a thermoplastic resin composition characterized in that the content of the hydroxyl group-containing unsaturated compound in the entire composition is 0.5 to 15% by weight.

The styrene-based copolymer resin used in the present invention may contain maleimide as a monomer.

Hereinafter, the styrene-based copolymer resin containing maleimide as a monomer is abbreviated as “maleimide-based resin”.

The maleimide resin used in the present invention is obtained by polymerizing a maleimide compound, an aromatic vinyl compound and optionally other monomers copolymerizable therewith in the presence or absence of a rubbery polymer. It is a copolymer.

Examples of the rubbery polymer include ethylene-propylene random copolymers and block copolymers, ethylene-
Copolymers of ethylene and α-olefins such as butene random copolymers and block copolymers; ethylene-
Copolymers of ethylene and unsaturated carboxylic acid esters such as methacrylate and ethylene-butyl acrylate; Copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate; Ethylene-propylene-ethylidene norbornene copolymers, ethylene-propylene Ethylene-propylene-non-conjugated diene terpolymers such as hexadiene copolymers; polybutadiene, isoprene, styrene-butadiene random and block copolymers,
Acrylonitrile-butadiene copolymer, butadiene-
Diene rubbers such as isoprene copolymers; butylene-isoprene copolymers and the like, and these may be used alone or in combination of two or more.

Of these, preferred rubbery polymers in terms of impact resistance are ethylene-propylene rubber, ethylene-propylene-non-conjugated diene-polymer and diene rubber. More preferably polybutadiene and styrene-
It is a butadiene copolymer, and the styrene content in this styrene-butadiene copolymer is preferably 50% by weight or less.

The content of the rubbery polymer in the resin (a) is preferably 3 to 35% by weight, more preferably 5 to 35% by weight, and particularly preferably 5 to 33% by weight. If it is less than 3% by weight, impact resistance is poor, and if it exceeds 35% by weight, moldability is poor and heat shrinkage becomes large.

Examples of the maleimide compound used in the present invention include maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-o-chlorophenylmaleimide, N-cyclohexylmaleimide, etc., and particularly preferred. Is N-phenylmaleimide,
Examples thereof include N-o-chlorophenylmaleimide and N-cyclohexylmaleimide, and these may be used alone or in combination of two or more.

As the aromatic vinyl compound, styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene,
Dibromostyrene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene, o-methylstyrene, p
-Methylstyrene, dimethylstyrene and the like, and these may be used alone or in combination of two or more.
Of these, the aromatic vinyl compound preferably used is styrene, and when two or more aromatic vinyl compounds are used together, it is preferable to use styrene in a proportion of 50% by weight or more.

Examples of other copolymerizable monomers include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, and methacrylic acid esters such as methyl methacrylate and ethyl methacrylate. These are used alone or in combination of two or more.

Specific combinations of the monomers other than these maleimide compounds are shown below.

Styrene Styrene-acrylonitrile Styrene-methyl methacrylate Styrene-acrylonitrile-methyl methacrylate Further, by substituting α-methylstyrene for part or all of these styrenes, a maleimide copolymer having high heat resistance can be obtained.

Furthermore, flame retardancy can be imparted by replacing part or all of styrene with halogenated styrene.

Here, the composition ratio of the maleimide compound and the aromatic vinyl compound in the maleimide copolymer is 70/30 to 1 by weight.
It is in the range of 0/90, preferably 60/40 to 20/80. If the maleimide compound is less than 10% by weight, the heat resistance is low, and if it exceeds 70% by weight, the moldability is deteriorated, which is not preferable.

Further, the maleimide-based resin of the present invention includes a rubber-modified graft resin obtained by polymerizing a monomer that becomes a resin component in the presence of a rubbery polymer and a resin that becomes a resin component in the absence of a rubbery polymer. It may be a composition with a resin obtained by polymerizing a monomer.

As a polymerization method for obtaining the maleimide resin used in the present invention, a bulk polymerization method, a solution polymerization method and the like are suitable, and a polymerization catalyst, a polymerization temperature and the like are used in a general vinyl monomer radical polymerization method. It can be the same as the one.

Styrenic resins that do not contain maleimide as a monomer are aromatic vinyl compounds, vinyl cyan compounds and other vinyl monomers copolymerizable with them in the presence or absence of a rubbery polymer. It is a resin obtained by polymerizing a resin component consisting of.

As the rubbery polymer and the aromatic vinyl compound, the same ones as those used in the above maleimide copolymer resin can be used.

Examples of the vinyl cyan compound include acrylonitrile and methacrylonitrile, and of these, acrylonitrile is preferable.

Other vinyl compounds copolymerizable with the aromatic vinyl compound and vinyl cyan compound include methyl acrylate, ethyl acrylate, propylene acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl. Alkyl esters of acrylic acid such as acrylate, octadecyl acrylate, phenyl metallate, benzyl acrylate; methyl methacrylate, ethyl methacrylate, propylene methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate. , Methacrylic acid alkyl esters such as kutadecyl methacrylate, phenyl methacrylate and benzyl methacrylate; unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride; unsaturated acids such as acrylic acid and methacrylic acid. These may be used alone or in combination of two or more. This other copolymerizable vinyl monomer is preferably incorporated in the resinous constituent in an amount of preferably 50% by weight or less, more preferably 20% by weight or less.

The styrene-based resin containing no maleimide as a monomer is a resin obtained by polymerizing a monomer of a resin component in the presence of a rubbery polymer, and a single resin component in the absence of a rubbery polymer. It may be a composition with a resin obtained by polymerizing a monomer.

More specifically, the styrene-based resin containing no maleimide as a monomer is specifically acrylonitrile-butadiene rubber-styrene resin (ABS resin), acrylonitrile-ethylene propylene rubber-styrene resin (AES resin), acrylonitrile-butadiene. Rubber-methyl methacrylate-styrene (ABSM resin), acrylonitrile-
Examples include styrene copolymer (AS resin), methyl methacrylate-styrene copolymer (MS resin), high-impact polystyrene (HIPS), acrylonitrile-n-butyl acrylate rubber-styrene resin (AAS resin). it can.

The styrene copolymer resin in the present invention is required to copolymerize a hydroxyl group-containing unsaturated compound.

The hydroxyl group-containing unsaturated compound is a compound having at least one unsaturated bond (double bond, triple bond) and containing a hydroxyl group. Typical examples thereof include an alcohol having a double bond, an alcohol having a triple bond, an ester of a monovalent or divalent unsaturated carboxylic acid and an unsubstituted dihydric alcohol, and an unsubstituted trivalent unsaturated carboxylic acid. Examples thereof include esters with polyhydric alcohols, esters with unsubstituted tetrahydric alcohols, and esters with unsubstituted pentavalent or higher alcohols.

Of the hydroxyl compounds used in the present invention, a typical example of a suitable compound is 3-hydroxy-1.
-Propene, 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-
Examples include tetrahydroxypentyl acrylate and 2,3,4,5-tetrahydroxypentyl methacrylate.

These are used alone or in combination of two or more. Preferred examples of the hydroxyl group-containing unsaturated compound include hydroxystyrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate. Particularly preferred is methacrylic acid-2-
It is hydroxyethyl.

When a styrene resin is copolymerized with a hydroxyl group-containing unsaturated compound, as a part to be copolymerized in each polymer, (1) a rubbery polymer (2) a graft layer of a graft polymer (3) a non-grafted styrene polymer Are preferred, but (2) or (3) is preferred, and (3) is more preferred.

The content of the hydroxyl group-containing unsaturated compound in the thermoplastic resin composition of the present invention is 0.5 to 15% by weight, preferably 1 to 10% by weight. If it is less than 0.5% by weight, impact resistance is not improved, which is not preferable. On the other hand, if it exceeds 15% by weight, moldability is deteriorated, which is not preferable.

Examples of the method for producing the styrene-based copolymer resin include emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization and the like of the monomer in the presence of the rubbery polymer. As the polymerization initiator, molecular weight modifier, emulsifier, dispersant, solvent, etc. used, those usually used can be used as they are. Preferably in the presence or absence of the rubbery polymer obtained by emulsion polymerization, a monomer, an additional emulsifier, a monomer, a polymerization initiator, 30 to 150 ° C., 1 to 15 hours, −
This is a method of mixing a graft product obtained by polymerization under the condition of 1.0 to 5 kg / cm ² with a styrene-based copolymer resin obtained by emulsion polymerization or solution polymerization.

The polyamide elastomer (b) used in the present invention includes an aminocarboxylic acid having 6 or more carbon atoms or a lactam as a hard segment or a nylon mn salt (X) having m + n ≧ 12, and a polyol as a soft segment, specifically, Is composed of poly (alkylene oxide) and glycol (Y), and the proportion of the component (X) in the total copolymer (b) is 95 to 10% by weight, preferably 90.
-20% by weight, more preferably 80-90% by weight. If the proportion of the component (X) in the total copolymer (b) exceeds 95, the flexibility is poor, and if it is less than 10% by weight, the chemical resistance is poor, which is not preferable.

The aminocarboxylic acid having 6 or more carbon atoms, the lactam, or the nylon mn salt (X) having m + n ≧ 12 includes
Aminocarboxylic acids such as ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminobergonic acid, ω-aminocapric acid, 11-aminoudecanoic acid and 12-aminododecanoic acid, or caprolactam, laurolactam and the like. Lactam and nylon 6.6, 6.1
0, 6/12, 11/6, 11/10, 11/12, 12/6, 12/1
Nylon salts such as 0, 12 and 12 are listed.

Examples of the poly (alkylene oxide) glycol (Y) include polyethylene glycol, poly (1,2 and 1,3 propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide).
Examples thereof include glycol, a block or random copolymer of ethylene oxide and propylene oxide, and a block or random copolymer of ethylene oxide and tetrahydrofuran. Their average molecular weight is 500-3000.

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

The bond between the component (X) and the component (Y) may be an ester bond or an amide bond depending on the terminal group of the component (b).
A third component such as dicarboxylic acid or diamine can be used depending on the bond.

As a specific synthesis method, for example, Japanese Examined Patent Publication No. 56-45410,
The method disclosed in JP-A-55-133424 can be used.

The dicarboxylic acid has 4 to 20 carbon atoms,
Examples include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4-dicarboxylic acid, diphenoxyethanedicarboxylic acid, and sodium 3-sulfoisophthalate. Alicyclic dicarboxylic acids such as aromatic dicarboxylic acids, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4-dicarboxylic acid and succinic acid, oxalic acid, adipic acid, sebacic acid And aliphatic dicarboxylic acids such as dodecanedicarboxylic acid.

As the diamine, aromatic, alicyclic, or aliphatic diamine is used. Specifically, as the aliphatic diamine,
Hexamethylenediamine is considered.

The mixing ratio of the styrene-based copolymer resin (a) obtained by copolymerizing a hydroxyl group-containing unsaturated compound and the polyamide elastomer (b) is 99/1 to 5/95 (weight% ratio). Preferably 95/5 to 10/90 (% by weight ratio), more preferably 90 /
It is 10 to 90/90 (weight% ratio). When the content of the polyamide elastomer is 10% by weight or more, a composition having further excellent heat resistance, impact resistance, moldability and chemical resistance can be obtained. If the polyamide elastomer is less than 1% by weight,
Moldability and chemical resistance are not good. Further, if it exceeds 95% by weight, heat resistance and impact resistance decrease.

A conventional method is used for mixing the components (a) and (b) of the composition of the present invention. For example, each component is mixed with a mixer, and then melt-kneaded at 200 to 280 ° C. with an extruder to granulate.

More simply, the components can be directly melt-kneaded and molded in a molding machine.

Compositions of the invention include antioxidants such as 2,6-di-t.
-Butyl-4-methylphenol, 2- (1-methylcyclohexyl) -4,6-dimethylphenol, 2,2-methylene-bis- (4-ethyl-6-t-butylphenol), 4,4'-thiobis -(6-t-butyl-3-methylphenol), dilaurylthiodipropionate, tris (di-nonylphenyl) phosphite, wax;
UV absorbers such as p-t-butylphenyl salicylate, 2,2'-dihydroxy-4-methoxybenzophenone, 2- (2'-hydroxy-4'-n-octoxyphenyl) benzotriazole; lubricants such as paraffin Wax, stearic acid, hydrogenated oil, stearamide,
Methylenebis stearamide, n-butyl stearate, ketone wax, octyl alcohol, lauryl alcohol, hydroxystearic acid triglyceride; flame retardants such as antimony oxide, aluminum hydroxide, zinc borate, tricresyl phosphate, tris (dichloropropyl). Phosphates, chlorinated paraffins, tetrabromobutane, hexabromobenzene, tetrabromobisphenol A; antistatic agents such as stearoamidopropyldimethyl-β-hydroxyethylammonium nitrate; colorants such as titanium oxide, carbon black; fillers , For example calcium carbonate, clay, silica,
Glass fibers, glass spheres, carbon fibers; pigments and the like can be added as necessary.

e. Examples Next, the present invention will be described in more detail with reference to Examples. In the following text, parts and% indicate parts by weight and% by weight.

Production Example 1 Using a 10-liter autoclave equipped with a stirrer and a thermometer, 60 parts of toluene and the components shown in Table 1 are shown in Table-1.
And a sufficient solution at room temperature to form a uniform solution. After that, the temperature is raised so that the internal temperature of the reactor becomes 10
When the temperature reached 0 ° C, a solution prepared by dissolving 0.25 part of dicumyl peroxide in 10 parts of toluene was added to initiate polymerization.
When the polymerization was carried out while maintaining the polymerization temperature at 120 ° C., the yield reached almost 100% 8 hours after the initiation of the polymerization.

The obtained polymer solution was poured into water, and the solvent and residual monomers were removed by passing steam through the polymer solution.

The polymer from which the solvent and the monomer were removed was pulverized and dried to obtain the samples (G-1 to G-3 and M-1 to M-8) shown in Table 1.

Production Example 2 Each chemical was charged into a 7-liter glass flask equipped with a stirrer by the compounding treatment shown in Table-2, and the inside of the reactor was replaced with nitrogen, and then the temperature of the heating jacket was controlled to 70 ° C while controlling the internal temperature. Was heated to 40 ° C., 0.3 parts of sodium pyrophosphate dissolved in 10 parts of water, 0.35 parts of dextrose, 0.01 part of ferrous sulfate and 0.1 minute of cumene hydroperoxide were added and reacted. One hour after the reaction was started, the additional addition mixture shown in Table 2 was continuously added over 3 hours, and the reaction was continued for another 1 hour.

After adding 1.0 part of 2,6-di-tert-butylparacresol as an anti-aging agent to the obtained graft polymer latex, sulfuric acid (2 parts to 100 parts of polymer) was added, and 9
Solidified at 0 ° C. The coagulated product was separated, washed with water, dehydrated and dried to obtain graft polymers G-4 and G-5 shown in Table-2.

Production Example 3 A 7-liter glass flask equipped with a stirrer was charged with each chemical by the compounding treatment shown in Table 2, and the inside of the reactor was replaced with nitrogen. Then, the temperature of the heating jacket was controlled to 70 ° C and the internal temperature was adjusted. Was heated to 50 ° C., 0.3 parts of potassium persulfate dissolved in 4 parts of water, and 0.1 part of sodium sulfite dissolved in 1 part of water were added and reacted for 3 hours.

Calcium chloride (2 parts per 100 parts of polymer) was added to the obtained styrene-based polymer latex, and the temperature was 90 ° C.
It was solidified with. The coagulated product was separated, washed with water, dehydrated and dried to obtain styrene-based polymer M-9 to M-14 shown in Table 2.

Production Example 4 Polyamide elastomers PAE-A and B were synthesized as lauryl lactam 40% by weight, 73% by weight, polytetrahydrofuran 46% by weight, 23% by weight, and dodecanedicarboxylic acid 14% by weight, 4% by weight, respectively.

Examples 1 to 24 and Comparative Examples 1 to 15 The components shown in Table 4 were melt-kneaded at a temperature of 250 ° C with a 50 mm extruder to prepare pellets. Using this pellet,
The melt flow index (measurement condition: 240 ° C., 10 kg) was measured according to JIS K7210.

Also, from the above pellets, a 5oz injection molding machine (Toshiba Corp. I
S-125A) was molded at a molding temperature of 220 ° C to prepare a test piece, and the Izod impact strength (ASTM D256, 1/4 "notch, 23 ° C) was measured.

Also, the test piece (1/8 ″ × 1/2 ″ × 5 ″) is left at 100 ° C. for 2 hours, then returned to room temperature, and the heat shrinkage ratio is measured.
It was used as an index of heat resistance.

Furthermore, the test piece (1/8 "x 1/2" x 5 ") has a strain rate of 1%
Dioctyl phthalate (abbreviated as DOP) was applied to the slack portion by applying a constant strain, and the time until rupture was measured by leaving it at 23 ° C. and used as an index of chemical resistance.

Also, the static charge decay rate can be measured by STATIC HONESTOMETER (SHI
SIDO Co. Ltd) was used to apply a voltage of 8 kV to the test piece for 1 minute, after which the voltage was removed and the amount of charge was measured, and the time until it became half the initial amount was measured. This was defined as the half-life value (sec).

 The smaller this value, the better the antistatic property.

f. Effect of the Invention The thermoplastic resin composition of the present invention has a much higher impact resistance than the conventional maleimide-based resin or styrene-based resin and polyamide-based elastomer composition, and heat resistance and molding. Excellent processability, chemical resistance and antistatic properties. Thus, the thermoplastic resin composition of the present invention is a material having a high level of balance of various physical properties,
It is an excellent resin material that can meet the recent strict quality requirements.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication location C08L 35/06 LJW 51/00 LKP 77/00 LQS (72) Inventor Tadahiko Tsutsumi Tsukiji, Chuo-ku, Tokyo 2-11-24, Japan Synthetic Rubber Co., Ltd. (56) Reference JP 61-157552 (JP, A) JP 60-170646 (JP, A) JP 60-55054 (JP, A) ) JP-A-61-73765 (JP, A)

Claims (3)

[Claims] 1. A composition comprising (a) 5 to 99% by weight of a styrene-based copolymer resin copolymerized with a hydroxyl group-containing unsaturated compound and (b) 2 to 95% by weight of a polyamide-based elastomer, and comprising A thermoplastic resin composition, wherein the content of the hydroxyl group-containing unsaturated compound is 0.5 to 15% by weight. 2. The thermoplastic resin composition according to claim 1, which contains maleimide as a monomer in the styrene copolymer resin. 3. The styrene-based copolymer resin is a hydroxyl group-containing unsaturated compound, an aromatic vinyl compound, and, if necessary, a vinyl cyanide compound or the presence thereof in the presence or absence of a rubbery polymer. The thermoplastic resin composition according to claim (1), which is a polymer of a monomer composed of another copolymerizable vinyl compound.