JPH02263861A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition having excellent heat resistance and moldability, comprising polyphenylene ether resin, a polyester derived from cyclohexane dimethanol and a rubbery elastomer and/or a moldified rubber elastomer. CONSTITUTION:A thermoplastic resin composition comprises (A) polyphenylene ether resin, (B) a polyester resin derived from cyclohexanedimethanol, preferably a polyester resin mainly comprising repeat units of the formula (the substituted cyclohexane ring is cis and/or trans isomer; R is 6-20C six carbon-membered cyclic dicarboxylic acid residue) and (C) a rubbery elastomer and/or a modified rubber elastomer, preferably a graft copolymer prepared by grafting one kind or more of vinylic monomers to a complex rubber having a structure wherein 1-99wt.% of a polyorganosiloxane rubber and 99-1wt.% of a polyalkyl (meth) acrylate rubber are mutually entangled, the component C being contained in an amount of 1-50wt.% based on the whole composition.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides a novel thermoplastic comprising a polyphenylene ether resin, a polynisal resin derived from cyclohexanediol, and a rubber-like elastic body and/or a modified rubber-like elastic body. The present invention relates to a resin composition.

[Conventional technology]

Polyphenylene ether has excellent, well-balanced properties across the board, including mechanical properties, electrical properties, flame retardance, heat resistance, and water resistance, and has good moldability and is used in many applications as an engineering plastic. It is being

On the other hand, polyester resin is an engineering plastic that has excellent moldability, heat resistance, and organic solvent resistance.

Many attempts have been made to blend polyphenylene ether resins and polyester resins, but in general, the molding temperatures of polyphenylene ether resins are 300°C or higher, while the molding temperatures of polyester resins are low (e.g., The upper limit of the molding temperature for polybutylene terephthalate, which is a polyester resin, is 280°.
It is about C. ), therefore, the resin composition was not good in terms of heat resistance and moldability.

The present invention provides a thermoplastic resin composition based on a resin and a polyester resin.

[Means to solve the problem]

The present invention comprises (A) polyphenylene ether resin, (B)
It consists of a polyester resin derived from cyclohexanedimethanol, and (C) a rubbery elastomer and/or a modified rubbery elastomer, and the amount of component (C) is 1 to 50% by weight based on the weight of the total resin composition. , to provide a thermoplastic resin composition with excellent heat resistance.

The polyphenylene ether resin used in the present invention is a homopolymer or copolymer formed by the following general formula.

[Problem to be solved by the invention]

The purpose of the present invention is to solve the above-mentioned problems and to obtain polyphenylene ether trees (in the formula: Q, -
(Q and Q are each independently selected from the group consisting of hydrogen and hydrocarbon groups, and m represents a number of 30 or more) Examples of the polyphenylene ether resin include poly(
2,6-dimethyl-1,4-phenylene) ether, poly(2,6-danityl-1,4-phenylene) ether, poly(2,6-diprobyl-1,4-)unisine) ether, poly(2,6-diprobyl-1,4-phenylene) ether, -Methyl-6-ethyl-1,4-phenylene) ether, poly(2-methyl-6-broby-1,4-phenylene) ether, poly(2-ethyl-6
-broby-1,4-phenylene)ether, (2゜6
-Simethyl-1,4-phenylene)ether and (2,3
',6-)trimethyl-1,4-phenylene) ether copolymer, (2,6-dinityl-1゜4-)unicine)ether and (2,3,6-)trimethyl-1,4 -phenylene) ether, and a copolymer of (2,6-dimethyl-1,4-phenylene) ether and (2,3,6-dryethyl-1,4-phenylene) ether. In particular, poly (2,6-cymethyl-1.4
-phenylene)ether, and (2,6-cymethyl-1
．． A copolymer of (4-phenylene) ether and (2,3,6-drimethyl-1,4-phenylene) ether is preferred, and more preferably a copolymer of poly(26-dimethyl-1,4-phenylene) ether.
-phenylene) ether.

The degree of polymerization of the polyphenylene ether resin used in the present invention is not particularly limited, but one having a reduced viscosity of 0.3 to 0.7 j/g at 25° C. in a chloroform solvent is preferably used.

If it is less than 0.3 a/g, thermal stability will be poor, and if it is more than 0.1 dl/g, melt fluidity will be impaired.

The polyester used in the present invention is preferably obtained by condensation of the cis or trans isomer of 1,4-cyclohexanedimethanol (or a mixture thereof) with a carbon six-membered dicarboxylic acid and has the following formula ( I[
) is a polyester having a repeating unit represented by:

In formula (II)! The substituted cyclohexane ring is a cis or trans isomer or a mixture thereof, and R represents an organic group having 6 to 20 carbon atoms which is a decarboxylated residue derived from a six-membered carbon dicarboxylic acid.

A suitable polyester resin is derived from the reaction of the cis or trans isomer of 1,4-cyclohexanedimethanol or a mixture thereof with a mixture of isophthalic acid and terephthalic acid.

The polyester has a repeating unit represented by the following formula (III).

It can be manufactured by such a method.

The polyester resins used in the present invention also include those obtained by co-condensing 1°4-cyclohexanedimethanol and small amounts of other difunctional glycols with six-membered carbon dicarboxylic acids. Such other difunctional glycols include polymethylene glycols having 2 to 10 or more carbon atoms, such as ethylene glycol, butylene glycol, and the like.

Examples of carbon six-membered dicarboxylic acids in which the carboxyl group is bonded to the carbon six-membered ring residue represented by R in formula 1 at the distal position include terephthalic acid, trans-hexahydroterephthalic acid, p .

p'-Sulfonyl Nibenzoic Acid, 4,4'-Diphe These polyesters are well known in the art and are described, for example, in U.S. Pat.
-carboxyphenoxy)ethane, 4°4'-dicarboxydiphenyl ether, and mixtures thereof. All of these acids contain at least one carbon six-membered ring. Fused rings are also included, as in the case of 1,4- or 1,5-naphthalene dicarboxylic acids. As carbon six-membered dicarboxylic acids, those containing a trans-cyclohexane nucleus or those containing an aromatic nucleus with one or two benzene rings (at least one with normal benzenoid unsaturation) suitable. Fused or connected rings are also included. Although all of the compounds listed here are suitable examples, a particularly preferred dicarboxylic acid is terephthalic acid or a mixture of terephthalic acid and isophthalic acid.

The polyester has an intrinsic viscosity of 25-30% in 40% tetrachloroethane 760% phenol solution or similar solvent.
Preferably, the amount is in the range of 0.40 to 2.0 dl/g when measured at °C. Particularly suitable polyesters have intrinsic viscosities in the range 0.6 to 1.2 a/g.

The thermoplastic resin of the present invention may contain resin components other than polyphenylene ether resin (A) and polyester resin CB) as long as they do not impair the purpose of the invention. For example, aromatic alkenyl resins, especially polystyrene resins, It has good miscibility with polyphenylene ether resin and can be blended for the purpose of improving fluidity.

The rubber-like elastic body (C) used in the present invention can be used at room temperature (20 to
refers to natural and synthetic polymeric materials that are elastic at 25°C). Examples of suitable rubber-like elastomers include natural crepe rubber, synthetic rubber of the SBR type obtained by emulsion polymerization of butadiene and styrene, synthetic rubber of the GR-N type prepared from butadiene and acrylonitrile, polychlorobutadiene. , polyisobutylene, copolymers of isobutylene and butadiene or isobutylene, polyisobutylene, copolymers of ethylene and propylene, copolymers of ethylene-propylene and dienes, acrylic rubber,
Copolymers of dienes and various monomers (for example, unsaturated alkyl esters such as acrylic acid esters), epichlorohydrin rubber, silicone rubber, silicones and various monomers (for example, unsaturated carboxylic acids such as acrylic acid alkyl esters) Composite rubbers with alkyl esters of

A suitable rubber-like elastic body (C) is a composite rubber of silicone rubber and alkyl (meth)acrylic acid ester. A particularly preferable rubber-like elastic body has a structure in which silicone rubber and (meth)acrylic acid alkyl ester are intertwined with each other and are virtually inseparable, and the particle size is 00 l.
- It is obtained by graft polymerizing one or more types of vinyl monomers to a composite rubber having a diameter of ~1μ.

More generally, preferred rubber-like elastic bodies (C) are:
The polyorganosiloxane rubber component is 1 to 99% by weight, more preferably 10 to 90% by weight, and the polyalkyl (meth)acrylate rubber component is 99 to 1% by weight, more preferably 9% by weight.
One or more types of vinyl are added to a composite rubber composed of 0 to 10% by weight, which has a structure in which both rubber components are intertwined with each other and are virtually inseparable, and whose average particle size is 0.1 to 1.0μ. It is a copolymer obtained by graft polymerizing monomers.

By using the above-mentioned composite rubber, it is possible to obtain a resin composition that provides a molded product with excellent impact resistance and molded surface appearance. In this composite rubber, if the proportion of the polyalkyl (meth)acrylate rubber component becomes extremely high, the impact resistance will decrease.

The average particle diameter of the composite rubber is preferably in the range of 0.1 to 1.0. If the average particle diameter is less than 0.1, the impact resistance of the molded product obtained from the resin composition deteriorates. However, if the average particle diameter exceeds Q4, the surface appearance of the molded product will deteriorate.

Emulsion polymerization is optimal for producing composite rubber having such an average particle size. In particular, we first create a polyorganosiloxane rubber latex, then alkyl (meth)
A preferred method is to swell and polymerize raw materials for acrylate rubber synthesis into polyorganosiloxane rubber particles.

The polyorganosiloxane rubber component constituting the above-mentioned composite rubber is synthesized from the organosiloxane and crosslinking agent shown below, and a graft crosslinking agent may also be used in combination. Examples of the organosiloxane include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trinotyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclo Examples include tetrasiloxane, which may be used alone or in combination of two or more. These components 1 are used in an amount of 50% by weight or more, preferably 70% by weight or more in the polyorganosiloxane rubber component.

Examples of crosslinking agents include trifunctional or tetrafunctional silane crosslinking agents, such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetrabutoxysilane. Tetraethoxysilane is particularly preferred.

The amount of crosslinking agent used is 0 in the polyorganosiloxane rubber component.
．． It is 1 to 30% by weight.

As a graft cross-agent, the general formula % formula % () (in each formula, R1 is a methyl group, ethyl group, propyl group or phenyl group, Rz is a hydrogen atom or a methyl group, n is o
, ' t or 2, p represents a number from 1 to 6) Compounds capable of forming an organosiloxane unit, etc. are used. (Meth)acryloyloxysiloxane, which can form the unit of general formula (IV), has a high grafting efficiency and can form effective graft chains, which is advantageous in terms of impact resistance. In addition, the general formula (IV
) is particularly preferred as a methacryloyloxysiloxane that can form the unit. The amount of grafting agent used is 0 to 10 in the polyorganosiloxane rubber component.
Weight%.

The preparation of this polyorganosiloxane rubber component is described, for example, in U.S. Pat.
The polymerization method described in Specification No. 5 and the like can be used.

The polyorganosiloxane rubber component is produced by, for example, shear-mixing a mixed solution of an organosiloxane, a grafting agent, and a crosslinking agent with water using, for example, a homogenizer in the presence of a sulfonic acid emulsifier such as alkylbenzenesulfonic acid or alkylsulfonic acid. Alkylbenzenesulfonic acid, which is preferably produced by the method described above, is suitable because it acts as an emulsifier for organosiloxane and also serves as a polymerization initiator. At this time, it is preferable to use an alkylbenzenesulfonic acid metal salt, an alkylsulfonic acid metal salt, or the like in combination, since this is effective in maintaining the polymer stably during graft polymerization.

Next, the polyalkyl (meth)acrylate rubber component constituting the above composite rubber is synthesized from the alkyl (meth)acrylate shown below, a crosslinking agent, and a grafting agent.

Examples of alkyl (meth)acrylates include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate; hexyl methacrylate; 2-ethylhexyl methacrylate;
Alkyl methacrylates such as n-lauryl methacrylate can be mentioned, with n-butyl acrylate being particularly preferred.

Examples of the crosslinking agent include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1.
Examples include 4-butylene diol dimethacrylate.

Examples of the graft crosslinking agent include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, and the like, and these crosslinking agents and graft crosslinking agents may be used alone or in combination of two or more. The total amount of these used is 0.1 to 20% by weight in the polyalkyl (meth)acrylate rubber component.

The polymerization of the polyalkyl (meth)acrylate rubber component is
The above alkyl (
After adding meth)acrylate, a crosslinking agent, and a grafting agent and swelling them into the polyorganosiloxane rubber particles, a normal radical polymerization initiator is applied to the crosslinked network of the polyorganodaloxane rubber as the zero polymerization progresses. A crosslinked network of polyalkyl (meth)acrylate rubber entangled with each other is formed, and composite rubber particles of a polyorganosiloxane rubber component and a polyalkyl (meth)acrylate rubber component that are substantially inseparable are obtained.

The composite rubber created by emulsion polymerization in this way is
It can be graft copolymerized with vinyl monomers, and can also be graft copolymerized with polyorganosiloxane rubber components and polyalkyl (meth)
Because it is tightly intertwined with the acrylate rubber component,
It cannot be extracted and separated using ordinary organic solvents such as acetone and toluene. 100' with this composite rubber apricot toluene solvent
The gel content after extraction with C for 12 hours is 80% by weight or more.

The vinyl monomer to be graft-polymerized to this composite rubber includes aromatic monomers such as styrene, α-methylstyrene, methyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, acrylonitrile, and methacrylonitrile. Various vinyl monomers such as alkenyl compounds, methacrylic esters, and acrylic esters may be mentioned, and these may be used alone or in combination of two or more. Among these vinyl monomers, styrene is particularly preferred.

The ratio of the vinyl monomer to the composite rubber is 30 to 95% by weight of the composite rubber based on the weight of the graft copolymer;
The vinyl monomer content is preferably 5 to 70% by weight.

If the vinyl monomer content is less than 5% by weight, the graft copolymer will not be sufficiently dispersed in the resin composition;
If it exceeds this, the impact strength development property will decrease.

The composite rubber-based graft copolymer latex can be obtained by polymerizing the above-mentioned vinyl monomers in one stage or in multiple stages using a radical polymerization technique.

The composite rubber graft copolymer latex thus obtained is poured into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved, and is salted out and coagulated to form a composite rubber graft copolymer latex. The polymer can be separated and recovered.

By distributing this composite rubber-based graft copolymer (C) to the above-mentioned thermoplastic polymer in the range of 1 to 50% by weight in the total resin composition, unprecedentedly high thermal stability and good weather resistance can be achieved. A thermoplastic resin composition can be obtained which has the following properties and also has excellent impact resistance.

The resin composition in the resin composition of the present invention can be selected from a wide composition range. Specifically, (A)
Based on the total amount of polyphenylene ether resin, (B) polyester resin derived from cyclohexanedimethanol, and (C) rubber-like elastic body, polyphenylene ether resin 10 to 90% by weight polyester resin derived from cyclohexanedimethanol 10 to 90% by weight The rubber-like elastic material may be contained in an amount of 90% by weight or a modified rubber-like elastic material in a range of 1 to 50% by weight, and more preferably in a range of 5 to 30% by weight. If the content of the rubber-like elastic body exceeds 50% by weight, the mechanical strength of the molded product obtained from the resin composition will decrease, which is undesirable, and if the ratio of polyester resin to polyphenylene ether resin is extremely high, the resin composition will deteriorate. heat resistance decreases.

The resin composition of the present invention can be used in Pan Bali mixers, roll mills,
It can be prepared by mechanical mixing using a known device such as a twin-screw extruder, and this composition is generally shaped into pellets.

Furthermore, the resin composition of the present invention may optionally contain a stabilizer,
Plasticizers, lubricants, flame retardants, l1i11, fillers, etc. may be blended. Specifically, stabilizers such as triphenyl phosphite; lubricants such as polyethylene wax and polypropylene wax; phosphate flame retardants such as triphenyl phosphate and tricresyl phosphate; brominated retardants such as decabromo biphenyl and decabromo biphenyl ether; Fuel:
Examples include pigments such as titanium oxide, zinc sulfide, and zinc oxide; fillers such as glass fiber, asbestos, wollastonite, mica, and talc.

〔Example〕

The present invention will be specifically explained below using Examples.

The physical properties in each Example and Comparative Example were measured by the following methods.

Izot impact strength: Based on the method of STHD 256.

Heat sag: Hold a specimen with a width of 12.5 mm, length of 127 mm, and thickness of 3.2 mm in an oven at 150°C for 1 hour with an overhang of 100 mm. ) was measured.

Reference Example: Production of silicone/acrylic composite rubber graft copolymer (S-1) Mix 2 parts of tetraethoxysilane, 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane, and 97.5 parts of octamethylcyclotetrasiloxane. 100 parts of a siloxane mixture was obtained. Add 100 parts of the above mixed siloxane to 200 parts of distilled water in which 1 part each of sodium dodecylbenzenesulfonate and dodecylbenzenesulfonic acid were dissolved, and mix with a homomixer at 10.00O
After pre-stirring at 300 rpm,
Emulsification and dispersion were performed at a pressure of kg/c4 to obtain organosiloxane latex. This mixed solution was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 80°C for 5 hours while stirring and mixing, and then left at 20°C.
After 48 hours, the pH of this latex was neutralized to 6.9 with an aqueous sodium hydroxide solution to complete the polymerization and obtain polyorganosiloxane rubber latex-1. The polymerization rate of the obtained polyorganosiloxane rubber was 89.7%, and the average particle diameter of the polyorganosiloxane rubber was 0.16.

10% of the above polyorganosiloxane rubber latex-1
0 parts (solid content 30%) were collected, placed in a separable flask equipped with a stirrer, added with 120 parts of distilled water, replaced with nitrogen, heated to 50°C, and heated to 37% n-butyl acrylate.
5 parts, allyl methacrylate 2.5 parts and tert-
Add a mixture of 0.3 parts of butyl hydroperoxide 3
The mixture was stirred for 0 minutes to allow the mixture to penetrate into the polyorganosiloxane rubber particles. Then ferrous sulfate 0.0003
part, ethylenediaminetetraacetic acid disodium salt o, ooi
1 part, Rongalit 0.17 parts and distilled water 3 parts to start radical polymerization, and then the internal temperature was 70''C.
The mixture was held for 2 hours to complete polymerization and obtain a silicone/acrylic composite rubber latex. A portion of this latex was sampled and the average particle size of the composite rubber was measured and found to be 0.19 m. In addition, this latex is dried to obtain a solid substance,
After extraction with toluene at 90°C for 112 hours, the gel content was measured and found to be 90.3%. A mixture of 0.3 parts of Ler t-butyl hydroperoxide and 30 parts of styrene was added dropwise to this composite rubber latex at 70°C for 45 minutes, and then held at 70°C for 4 hours to carry out graft polymerization to the composite rubber. completed.

The polymerization rate of the obtained graft copolymer was 98.6%, and the gel content was 75%. The obtained graft copolymer latex was coagulated by dropping it into hot water containing 5% calcium chloride, separated, washed, and then dried at 75°C for 16 hours to form a silicone/acrylic composite rubber graft copolymer (
S-1) was obtained.

1 Consideration U Production of composite rubber graft copolymers (S-2) to (S-5) Using polyorganosiloxane rubber latex-1 prepared during the production of composite rubber broom graft copolymer S-1,
A composite rubber broom graft copolymer having a ratio of polyorganosiloxane rubber and butyl acrylate rubber different from that of (S-1) was produced as follows.

That is, composite rubber latexes (S-2) to (S-5) were prepared using a radical polymerization initiator in the same manner and under the same conditions as in Reference Example 1, except for the following formulations.

30 parts of styrene to each composite rubber latex, and tert.
- A mixed solution with 0.12 parts of butyl hydroperoxide was added, and a graft polymerization reaction was carried out on the composite rubber using the same conditions and method as in Reference Example 1 above. Similarly, a composite rubber band graft copolymer (hereinafter referred to as (S-2)) was obtained by coagulation, separation, and drying treatment.
~ (referred to as S-5)) was obtained.

Examples 1 to 4 Intrinsic viscosity at 25°C in chloroform is 0.5a/
gr poly(2,6-dimethyl-1,4-phenylene) ether and tetrachloride elas 240%/phenol 60%
Intrinsic viscosity measured in solution at 25°C is 1.0 dl/gr
Poly(1,4-cyclohexanedimethanol terephthalate-coisophthalate) and the silicone/acrylic composite rubber graft copolymer (S-1) obtained in Reference Example were mixed in the proportions shown in Table 1, and the mixture was heated at 280°C. It was extruded using a twin-screw extruder, and after cooling, it was cut into pellets. Using this pellet, test pieces were made using an injection molding machine, and the results shown in Table 1 were obtained.

Margins below Table 1 Table 2 Rubber (parts) 10"10" 3 Examples 5 to 7, Comparative Example 1 Poly(2,6-cymethyl-1.4-
Phenylene) ether, poly(1,4 cyclohexanedimethanol terephthalate-coisophthalate), and various rubbers shown in Table 2 were mixed in the proportions shown in Table 2, extruded in the same manner, molded, and tested. A piece was prepared and the results shown in Table 2 were obtained.

*1 SBS rubber (Califlex TR1101, manufactured by Shell Chemical ■) *2 Old PS (Nisbrite 500SB, manufactured by Nippon Polystyrene) $3flPDM (Tafmar A-4085, manufactured by Mitsui Petrochemical) Examples 8 to 11 Examples 1 to 4 Poly(2,6-cymethyl-1,4-
Phenylene) ether, poly(1,4-cyclohexanedimethanol terephthalate), and composite rubber graft copolymer were mixed in the proportions shown in Table 3, extruded and molded in the same manner, and tested. A piece was prepared and the results shown in Table 3 were obtained.

Table 3 Example Na 8 9 10 [Effects of the Invention] (A) Borifuenisin ether resin of the present invention, (B) Polyester resin derived from cyclohexanedimethanol, and (C) Rubber-like elastic body and/or modification A thermoplastic resin composition made of a rubber-like elastic body has excellent impact resistance, heat resistance, and organic solvent resistance, and is particularly suitable as a molding material that requires high heat resistance.

Claims (1)

[Claims] 1. (A) polyphenylene ether resin, (B) polyester resin derived from cyclohexanedimethanol, and (C) rubbery elastomer and/or modified rubbery elastomer in a total resin composition of 100%. A thermoplastic resin composition having excellent heat resistance and containing 1 to 50% by weight. 2. A type of composite rubber in which the modified rubber-like elastic body has a structure in which 1 to 99% by weight of a polyorganosiloxane rubber component and 99 to 1% by weight of a polyalkyl (meth)acrylate rubber component are intertwined with each other so that they cannot be separated. Alternatively, the resin composition according to claim 1, which is a composite rubber-based graft copolymer obtained by graft polymerization of two or more types of vinyl monomers. 3. The above polyester resin has the following formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. 2. A composition according to claim 1, which comprises as a main constituent a repeating unit of an organic group having 6 to 20 carbon atoms, which is a derived decarboxylated residue.