JPH0446956A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition excellent in impact resistance, heat resistance, chemical resistance, etc., by mixing a thermoplastic polyester resin, an aromatic polycarbonate resin, a rubber-toughened resin, and a specified polymer at a specified weight ratio. CONSTITUTION:The title composition is produced by mixing 2-96wt.% thermoplastic polyester resin (A), 2-96wt.% aromatic polycarbonate resin (B), 1-80wt.% rubber-toughened resin (C) obtained by polymerizing a monomer mixture composed mainly of a vinyl cyanide compound and/or an alkyl (meth)acrylate and an aromatic vinyl compound in the presence of a rubber component consisting mainly of an alpha-olefin copolymer and/or a hydrogenated conjugated diene polymer, and 1-50wt.% polymer (D) selected from an alpha-olefin copolymer, a block copolymer composed mainly of an aromatic vinyl compound and a conjugated diene compound, and a hydrogenated conjugated diene polymer so that the total of components A, B, C, and D is 100wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a thermoplastic resin composition having excellent solvent resistance, heat resistance, impact resistance, and molded product surface appearance.

[Conventional technology]

Traditionally, thermoplastic polyester resins such as polybutylene terephthalate and polyethylene terephthalate have been widely used as engineering plastics with excellent solvent resistance and fluidity, but they have low notched impact strength and high load resistance. It has the disadvantage that the lower heat distortion temperature is low.

On the other hand, aromatic polycarbonate resin is also widely known as an engineering plastic with excellent impact resistance and heat resistance, but due to its high melt viscosity, it has poor moldability and also has poor solvent resistance. It has the following drawbacks. In order to eliminate these mutual disadvantages, a composition in which a thermoplastic polyester resin and an aromatic polycarbonate are mixed has been proposed (Japanese Patent Publication No. 36-1403).
However, even this composition still has the drawback of low notched Izot impact strength.

The present inventors tried a method of blending an AES resin into the composition for the purpose of improving the notched isot impact strength, but it was still not satisfactory.

[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 solvent resistance, heat resistance, impact resistance, and surface appearance of molded products.

[Means to solve the problem]

The present invention comprises: (a) 2-96% by weight of thermoplastic polyester resin, (c) 2-96% by weight of aromatic polycarbonate resin, (c)
A vinyl cyanide compound and/or (meth)acrylic acid alkyl ester and an aromatic vinyl compound are mainly mixed in the presence of a rubber component mainly composed of a hydrogenated product of an α-olefin copolymer and/or a conjugated diene polymer. Rubber reinforced resins 1 to 80 obtained by polymerizing monomer mixtures as components
% by weight, and a small amount selected from (alpha-olefin copolymers, block copolymers whose main components are aromatic vinyl compounds and conjugated diene compounds, and hydrides of conjugated diene polymers).
The present invention provides a thermoplastic resin composition containing 1 to 50% by weight of one type of polymer ((a) + (c) + (c) = 100% by weight). .

The thermoplastic polyester resin as component (a) used in the present invention is composed of a dicarboxylic acid and a diol compound, and is a relatively high molecular weight, substantially linear thermoplastic polymer. Preferred include polymeric glycol esters of terephthalic acid and isophthalic acid.

Some of these polymers are already commercially available, but they can also be manufactured using known manufacturing techniques (such as U.S. Pat. No. 2.465.319 and U.S. Pat. No. 3,047,539). can. That is, it can be produced by alcoholysis of phthalate ester with glycol and subsequent polymerization reaction, and also by a method of producing free phthalic acid or its halogenated derivative and polymerization reaction by heating glycol, and similar methods thereof. It can also be manufactured by a manufacturing method.

Preferred thermoplastic polyester resins used in the present invention are:
It is composed of a high molecular weight polymeric glycol terephthalate having a repeating unit of the following general formula (a)-1, or a mixture of glycol isophthalate and these esters.

・ ・ ・ ・ ・(a)-1 Here, m is preferably an integer of 2 to 10, and particularly preferably 2 to 4 in view of the physical properties of the composition.

A copolymer of terephthalic acid and isophthalic acid containing up to 30% of isophthalic acid units can also be suitably used.

Particularly preferred thermoplastic polyester resins include polyethylene terephthalate 1 and poly 1°4-butylene terephthalate. Further, branched polyethylene terephthalate and branched poly 1,4-butylene terephthalate can also be used. Such a branched polymer may contain a small amount of a branching component having at least three ester-forming groups, for example up to 5 mol % based on the terephthalic acid units.

The branching component may be one that forms a branch in the polyol unit portion in addition to the acid unit portion of the polyester, or may be a mixture of both. Examples of such branching moieties include tri- or tetracarboxylic acids, such as trimesic acid, trimellitic acid, pyromellitic acid and their lower alkyl esters, or polyols, preferably tetrols, such as pentaerythritol and triols. , such as trimethylolpropane or dihydroxydicarboxylic acids and hydroxydicarboxylic acids and units derived therefrom, such as dimethylol hydroxyterephthalate. These branched polyesters can be manufactured by the same manufacturing method as the branched poly(1,4-butylene terephthalate) resin described in, for example, US Pat. No. 3,953.404.

The amount of thermoplastic polyester resin used in the composition of the present invention is 2 to 96% by weight, preferably 5 to 85% by weight, more preferably 10 to 70% by weight, particularly preferably 20 to 60% by weight. [However, (a) + (c) + (c
)+(b)=100% by weight, the same applies hereinafter].

If the content of component (a) is less than 2%, solvent resistance will deteriorate;
On the other hand, if it exceeds 96% by weight, impact resistance will be poor.

Next, the aromatic polycarbonate resin of component (2) is a linear or branched thermoplastic polycarbonate produced by reacting an aromatic dihydroxy compound or a small amount of a polyhydroxy compound with a diester of phosgene or carbonic acid. It is resin. This (b) thermoplastic polycarbonate resin has the following general formula (2)-1
, Φ)-2 is used.

- (Ar-A-Ar-0-C-0)n -・・
・ ・ ・(2)-1 (Ar-0-C-0) n − ・ ・ ・ ・ ・(2)-2 (wherein, Ar is a phenylene group, or an alkyl group, an alkoxy group, a halogen group, or a nitro group A is a phenylene group substituted by a carbon-carbon bond or an alkylidene group, a cycloalkylidene group, an alkylene group,
It represents a cycloalkylene group, an alkylene group, an azoimino group, a sulfur atom, an oxygen atom or a sulfoxide group, and n is at least 2. (2) Aromatic polycarbonate (resin) used in the present invention, preferably one in which Ar is a p-phenylene group and A is an isopropylidene group.

The amount of aromatic polycarbonate resin (c) used in the composition of the present invention is 2 to 96% by weight, preferably 5 to 8% by weight.
5% by weight, more preferably 10 to 70% by weight, particularly preferably 20 to 60% by weight; if it is less than 2% by weight, the resulting composition will have poor impact resistance, while if it exceeds 96% by weight, it will have poor solvent resistance. It becomes inferior to sex.

Next, (c) the rubber-reinforced resin is prepared by adding a vinyl cyanide compound and/or (meth)acrylic compound in the presence of a rubber component mainly composed of a hydride of an α-olefin copolymer and/or a conjugated diene polymer. It is a resin obtained by polymerizing a monomer mixture whose main components are an acid alkyl ester and an aromatic vinyl compound. This (c) rubber-reinforced resin can also be produced by a graft polymerization method in which the monomer mixture is graft-polymerized in the presence of the rubber component, or at least one monomer constituting the monomer mixture or the It can also be produced by a graft blend method in which a (co)polymer obtained by separately polymerizing a portion of a monomer mixture is blended.

The graft polymerization method is not particularly limited, and may include a solution polymerization method, a bulk polymerization method, a suspension polymerization method, a bulk-suspension polymerization method, and even a graft polymerization method in which emulsion polymerization is performed using a latex obtained by emulsifying the above rubber component. Any method such as a polymerization method can be adopted as necessary.

Here, α constituting the rubber component serving as the base material of component (c)
- Examples of the olefin copolymer include copolymers of two types of α-olefins and copolymers of two types of α-olefins and polyene.

The α-olefin used here is an unsaturated hydrocarbon compound having 2 to 20 carbon atoms, and specifically includes ethylene, propylene, 1-butene, 1-pentene, 1-hexene,
Examples include heptene-1,1,4-methylbutene-1,4-methylpentene-1, but ethylene, propylene, and butene-1,4-methylpentene-1 are particularly preferred, and ethylene and propylene are particularly preferred. be.

Further, as polyene compounds, 1,4-pentadiene, 1,5-hexadiene, 2-methyl-1,5-hexadiene, 3,3-dimethyl-1°5-hexadiene, 1
．． 7-octadiene, 19-decadiene, 6-methyl-1,5-hexadiene, 1,4-hexadiene, 7-
Methyl-1゜6-octadiene, 9-methyl-1,9-
Undecane, isoprene, 1,3-pentadiene, 1゜4,9-decatriene, 4-vinyl-1-cyclohexane, cyclopentadiene, 2-methyl 2゜5-norbornadiene, 5-methyl-2-norbornene, 5-ethylidene -2-norbornene, 5-isopropylidene-2-
Examples include norbornene, 5-isopropenyl-2-norbornene, dicyclopentadiene, and tricyclopentadiene, with 5-ethylidene-2-norbornene and dicyclopentadiene being preferred.

The α-olefin copolymer is preferably an ethylene-propylene copolymer such as an ethylene-propylene copolymer or an ethylene-phlohylene-borien copolymer.

The preferred weight ratio of ethylene and propylene is 90.
: 10-20 : 80.

The preferred iodine value of the α-olefin-polyene copolymer is 20-40.

In addition, the hydride of the conjugated diene polymer constituting the rubber component serving as the base material of component (c) may be mixed with at least one block α or block T as shown in the specific example below. A block copolymer comprising the following block β or block α/β, or (co) comprising block β or block α/β
Examples include hydrogenated polymers. That is,
α: aromatic vinyl compound polymer, β: conjugated diene compound polymer, β1: conjugated diene compound polymer with a vinyl bond amount of 20% by weight or more, β2: conjugated diene compound with a vinyl bond amount of less than 20% by weight polymer, α/β; random copolymer of aromatic vinyl compound/conjugated diene compound; T; tapered polymer that is a copolymer of a conjugated diene compound and an aromatic vinyl compound, and in which the aromatic vinyl compound gradually increases; For example, conjugated diene polymers having the following skeletons can be mentioned.

■α−β ■α−β−α ■α−β−T ■α−β, −β2 ■β ■α/β ■α−α/β ■α−α/β−T ■α−α/β− α [Phase] β2-β1-β2 ■γ-β @γ-β-T ■T-α/β-T [Stock] γ-α-β Additionally, the conjugated diene polymers have these basic skeletons. Examples include copolymers having repeating polymers and also those obtained by coupling them. α of ■ above
For structures of -β and -βt, patent application No. 63-2
85775 specification, and those having the structure β in (1) and α/β in (2) are disclosed in JP-A-63-127400.

Furthermore, the structures of α-α/β in (2) and α-α/β-γ in (2) are detailed in Japanese Patent Application No. 1-124429 and Japanese Patent Application No. 1-124430. ing.

Here, the aromatic vinyl compounds constituting the conjugated diene polymer include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, vinylxylene,
Monochlorostyrene, dichlorostyrene, monofuromstyrene, dibromostyrene, fluorostyrene, p-t
-Butylstyrene, ethylstyrene, vinylnaphthalene, divinylbenzene, ■, ■-diphenylstyrene, N
.

N-diethyl-p-aminoethylstyrene, N.

Examples include N-diethyl-p-amineethylstyrene and vinylpyridine, with styrene being particularly preferred.

In addition, examples of the conjugated diene constituting the conjugated diene polymer include 1,3-butadiene, isoprene, 2,3-
Dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3
Examples thereof include -butyl-1°3-octadiene, chlorobrene, etc., preferably 1,3-butadiene, isoprene, and more preferably 1,3-butadiene.

The content of aromatic vinyl compounds in the conjugated diene polymer is
60% by weight or less, preferably 40% by weight or less, 5 to 40% by weight when an aromatic vinyl compound is an essential component; if it exceeds 60% by weight, the hydride takes on resinous properties and the impact resistance decreases. do.

In addition, the conjugated diene polymer has a microstructure in which the amount of vinyl bonding metal such as 1.2-13.4- is preferably 10% by weight or more, more preferably 20 to 80% by weight,
Particularly preferred is 30 to 60% by weight. If this proportion is less than 10% by weight, the obtained hydride will take on resinous properties and the impact resistance of the finally obtained thermoplastic resin composition will decrease, which is not preferable.

The hydrogenated product of the conjugated diene polymer can be obtained by hydrogenating the conjugated diene polymer. Here, the hydrogenation rate is 70% or more, preferably 90% or more. If the hydrogenation rate is less than 70%, the weather resistance of the thermoplastic resin composition finally obtained is undesirable.

The hydride of the conjugated diene polymer preferably has a number average molecular weight of 5,000 to i, ooo, ooo, preferably 30,000 to 300.
．． If it is less than 5,000, the polymer will not become rubbery but liquid, while if it exceeds i, ooo, or ooo, the processability tends to decrease, which is not preferable. Furthermore, the ratio of the weight average molecular weight to the number average molecular weight of the hydride (M
w/Mn) is preferably 10 or less.

The method of hydrogenating the conjugated diene polymer is described in detail in, for example, JP-A-1-275605.

Among the rubber components that serve as the base material of the rubber-reinforced resin (component (c)), hydrides of conjugated diene polymers are preferred, and by using them, impact resistance, surface appearance of molded products, and weather resistance can be improved. An even more excellent thermoplastic resin composition of the present invention can be obtained.

The content of the rubber component in component (c) is preferably 5 to 60% by weight, more preferably 10 to 50% by weight.

On the other hand, examples of the vinyl cyanide compound in the monomer mixture constituting the rubber-reinforced resin (c) include acrylonitrile derivatives such as acrylonitrile and methacrylonitrile.

In addition, the (meth)acrylic acid alkyl esters in the monomer mixture include, for example, acrylic acid alkyl esters such as methyl acrylate and ethyl acrylate;
Examples include methacrylic acid alkyl esters such as methyl methacrylate, preferably methyl methacrylate.

Further, the aromatic vinyl compound constituting the monomer mixture is the same as the aromatic vinyl compound that may constitute the conjugated diene polymer.

Moreover, other monomers can be used in the monomer mixture constituting the rubber reinforced resin (c) as required. Other monomers include maleimide compounds such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-0-chlorophenylmaleimide, N-cyclohexylmaleimide,
By using these compounds in combination, the heat resistance of the resulting composition can be improved.

Furthermore, other monomers include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, and maleic acid; acid anhydrides such as maleic anhydride and itaconic anhydride; and 2-hydroxyethyl acrylate. , hydroxyl group-containing monomers such as 2-hydroxyethyl methacrylate, amino group-containing monomers such as allylamine, aminoethyl methacrylate, and aminostyrene, and epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate. and at least one selected from these
By using seeds in combination, the compatibility between the resin components constituting the composition of the present invention can be improved.

The composition of these monomer mixtures is such that the vinyl cyanide compound and/or the (meth)acrylic acid alkyl ester are
Preferably 5 to 50% by weight, more preferably 10 to 40% by weight, particularly preferably 20 to 40% by weight, aromatic vinyl compound is present in the mixture, preferably 50 to 95% by weight, even more preferably 60 to 90% by weight. The content is preferably 60 to 80% by weight, and the content of other monomers used as necessary is about 50% by weight or less.

The preferred grafting rate of component (c) is 20 to 90% by weight.
, more preferably 25 to 85%, particularly preferably 30%
~80%. Here, the graft ratio refers to the ratio of the copolymer component directly graft-bonded to the rubber with respect to the amount of rubber in the graft polymer.
It can be controlled by the amount of polymerization initiator, polymerization temperature, etc.

Further, the intrinsic viscosity [η] (measured at 30° C.) of the methyl ethyl ketone soluble portion of the matrix component (rubber component) of component (c) is 0.3 to 0.1 a/g.

(c) The rubber reinforced resin is a graft copolymer obtained by polymerizing a monomer mixture in the presence of the rubber component, or a graft copolymer obtained by polymerizing a part of the monomer mixture in the presence of the rubber component. It may also be a blend of polymers obtained by separately polymerizing the graft body and the remaining monomer mixture.

(c) Rubber reinforced resin used in the present invention is emulsion polymerized,
Manufactured by solution polymerization, suspension polymerization, etc.

(c) A preferred method for producing the rubber reinforced resin uses a monomer mixture and additional emulsifiers, monomers, and polymerization initiators in the presence of the rubber component, generally at a polymerization temperature of 30.
~150℃, polymerization time 1-15 hours, polymerization pressure car 1.0
Graft copolymerization is performed under conditions of ~5.0 kg/cj to obtain a graft copolymer (including ungrafted polymers), or a rubber component and a monomer obtained by emulsion polymerization or solution polymerization. It is produced by mixing the (co)polymer of the mixture.

The amount of the rubber reinforced resin (c) used in the composition of the present invention is 1 to 80% by weight, preferably 5 to 60% by weight, more preferably 10 to 30% by weight, and if it is less than 1% by weight, the impact resistance On the other hand, if it exceeds 80% by weight, the heat resistance will be poor, and both are not preferred.

Next, component (b) of the present invention is used to improve the impact resistance of the resulting composition, and is mainly composed of an α-olefin copolymer, an aromatic vinyl compound, and a conjugated diene compound. At least one kind of polymer selected from a block copolymer of , and a hydrogenated product of a conjugated diene polymer.

Here, the α-olefin copolymer constituting component (d) is the same as the α-olefin copolymer constituting the rubber component of the rubber reinforced resin (c), but in particular Mooney viscosity (ML ,.4.100℃) is preferably 30-1
50, more preferably 50 to 150, and when a value within this range is used, a composition with even better impact resistance can be obtained.

In addition, as a block copolymer mainly composed of an aromatic vinyl compound and a conjugated diene compound constituting component (d), examples of general formulas (A-B) p(A-B) p-A, (A-
B) p-X (where A is an aromatic vinyl compound polymer block, B is a block mainly composed of a conjugated diene compound polymer, P is an integer of 1 or more, and X represents a coupling agent residue) It is what is expressed.

In addition, the polymer block mainly composed of a conjugated diene compound means that the conjugated diene compound block contains a conjugated diene compound alone or a conjugated diene compound containing a conjugated diene compound in an amount of 60% by weight or more, preferably 80% by weight or more, and an aromatic vinyl compound. It may be a copolymer block with one or more so-called tapered blocks in which vinyl aromatic compounds are randomly bonded or gradually increased.

The vinyl aromatic compound and conjugated diene compound used here are the same as those used in the conjugated diene polymer constituting the rubber component (c).

The weight average molecular weight of the block copolymer constituting component (d) is preferably 10,000 to 500,000, more preferably 20,000 to so
o, ooo.

Not only one type of block copolymer may be used, but also a combination of block copolymers having different structures and different vinyl aromatic compound contents may be used.

Furthermore, (the hydride of the conjugated diene polymer constituting the four components is the same as the hydride of the conjugated diene polymer that becomes the rubber component of the rubber reinforced resin (c)).

Component (iii) is preferably a hydride of a conjugated diene polymer, and by using this, a thermoplastic composition with even better impact resistance, surface appearance of molded articles, and weather resistance can be obtained.

The amount of this component (b) used in the composition of the present invention is:
The amount is 1 to 50% by weight, preferably 3 to 40% by weight, and more preferably 5 to 20% by weight. If it is less than 1% by weight, the impact resistance will not be improved sufficiently, while if it exceeds 50% by weight, the surface of the molded product will deteriorate. Unfavorable because of poor appearance and heat resistance.

Next, in the composition of the present invention, as the component (e) below, if necessary, a functional group-containing olefin copolymer and a vinyl (co)polymer have a multiphase structure. A plastic resin can be blended.

Here, (e) the functional group-containing olefin copolymer constituting the multiphase thermoplastic resin refers to an olefin unit and an olefin copolymer selected from the group of, for example, a carboxyl group, an acid anhydride group, an oxazoline group, and an epoxy group. It is mainly composed of unsaturated compound units having at least one kind of functional group. This functional group-containing olefin copolymer is, for example, a binary, ternary or multi-component copolymer of an olefin and the unsaturated compound monomer or other unsaturated monomer produced by high-pressure radical polymerization; As the olefin in the copolymer, ethylene and propylene are preferred, with ethylene being particularly preferred. The functional group-containing olefin copolymer is preferably an ethylene-glycidyl methacrylate copolymer or an ethylene-maleic anhydride copolymer, particularly preferably an ethylene-glycidyl methacrylate binary copolymer. The amount of olefin in this copolymer is 60
~99.5% by weight, 0.0% by weight of unsaturated compounds containing functional groups. 5~
A copolymer containing 40% by weight and 0 to 39.5% by weight of other unsaturated monomers is preferable. Examples of carboxyl group-containing unsaturated compounds include acid anhydride group-containing compounds such as acrylic acid, methacrylic acid, and maleic acid. Examples of the unsaturated compound include maleic anhydride and itaconic anhydride; examples of the oxazoline group-containing unsaturated compound include vinyloxazoline; and examples of the epoxy group-containing unsaturated compound include glycidyl methacrylate and allyl glycidyl ether. Preferred functional groups are epoxy groups and acid anhydride groups.

In addition, (e) vinyl-based (co) in multiphase structure thermoplastic resin
Specifically, polymers include styrene, methylstyrene,
Aromatic vinyl compounds such as dimethylstyrene, ethylstyrene, isopropylstyrene, chlorstyrene, α-methylstyrene, α-ethylstyrene, methyl such as (meth)acrylic acid: propyl, isopropyl, butyl,
Esters such as 2-ethylhexyl, cyclohexyl, dodecyl or octadecyl, vinyl ethers such as vinyl methyl ether and vinyl ethyl ether, vinyl cyan compounds and acrylic acid amide compounds such as acrylonitrile and methacrylaterile, and maleimides such as phenylmaleimide and cyclohexylmaleimide. Examples include (co)polymers obtained by (co)polymerizing one or more kinds of compounds.

(e) The multiphase structure thermoplastic resin of the present invention contains vinyl (co)I in the specific functional group-containing olefin copolymer.
Those with a structure in which F polymer is dispersed, or vinyl-based (
It consists of a co)polymer having a structure in which a specific functional group-containing olefin copolymer is dispersed.

The particle size of the dispersed (co)polymer is 0.001~
10t1m, preferably 0.01 to 5μm, and 0.
If it is less than 0.001 μm, or if it exceeds 10 μm, the mechanical strength of the resulting composition will decrease, which is undesirable.

The number average degree of polymerization of the vinyl (co)polymer in the component (e) is 5 to 10,000, preferably 10 to 5.000.
is within the range of

The grafting method for producing component (e) may be any commonly known method such as the chain transfer method or the ionizing radiation method, but the most preferred method is the method disclosed in Japanese Patent Application Laid-open No. 6
This is the method described in Publication No. 4-48856. In addition, (e)
In the components, the amount of the vinyl (co)polymer grafted to the functional group-containing olefin copolymer, that is, the grafting ratio, is preferably at least 1% by weight or more.

The amount of component (e) used in the composition of the present invention is usually
The content is 50% by weight or less, preferably 0.5 to 40% by weight, particularly preferably 0.5 to 20% by weight, and if it exceeds 50% by weight, heat resistance will be poor and therefore undesirable.

Next, when obtaining the thermoplastic resin composition of the present invention, (c
) component and/or (6) component can be crosslinked.

As the crosslinking means used here, peroxide crosslinking, resin crosslinking, sulfur crosslinking, etc., which are used for ordinary rubber, are used. As for specific crosslinking agents, for example, the crosslinking agents, crosslinking aids, crosslinking accelerators, etc. described in "Crosslinking Agent Handbook (written by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha)" are used. Crosslinking methods include, for example, a static crosslinking method in which components (a) to (d) and, if necessary, component (e) are kneaded and then crosslinked using a hot press, and a method in which a crosslinking agent is added and melt-mixed. Although there are dynamic crosslinking methods in which crosslinking is carried out while maintaining the state, the dynamic crosslinking method is preferred because of its excellent performance.

In the dynamic crosslinking method, the crosslinking agent includes components (a) to (d),
Further, if necessary, all components of component (e) may be added at the same time, or any component or part of all components may be mixed with a crosslinking agent, and the remaining components may be added later. Further, after melt-mixing all or part of each component, and further adding the remaining components, a crosslinking agent may be added to crosslink.

A composition suitable for crosslinking by adding the crosslinking agent is preferably a composition in which the total amount of components (a) and (2) in all components is 501% by weight or less, more preferably 45% by weight.
These are as follows.

The thermoplastic resin composition of the present invention can be obtained by kneading the above-mentioned components using various extruders, Banbury mixers, kneaders, rolls, etc. The order of addition of each component during melt-kneading is not particularly limited, but methods include a method of mixing and kneading all the components, a method of kneading arbitrary components, and then adding and kneading the remaining components.

When using the thermoplastic resin composition of the present invention, various fillers can be added.

For example, glass fiber, carbon fiber, metal fiber, gas beads, glass plastic, wollastonite, calcium carbonate, talc, barium sulfate, mica, potassium titanate whisker, fluororesin, molybdenum disulfide, carbon black, oxide Fillers such as titanium can be used alone or in combination. Among these fillers, those in the form of fibers such as glass fibers and carbon fibers preferably have a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more. These fillers can be used in an amount of 5 to 150 parts by weight based on 100 parts by weight of the composition of the present invention.

Furthermore, the thermoplastic resin composition of the present invention may contain additives such as known flame retardants, antioxidants, foaming agents, lubricants, plasticizers, pigments, and dyes. Preferred flame retardants are red phosphorus and halogen-based flame retardants, more preferably decabromidiphenyl ether, brominated polystyrene, brominated polyphenylene ether, a combination of brominated epoxy oligomer and antimony trioxide.

Further, a preferred lubricant is a montan wax. Furthermore, other polymers may be used depending on the required performance, such as ABS resin, MBS resin, As resin, HIPS, polystyrene, polysulfone, polyethersulfone, polyimide, and PPS.

Polyether ether getone, vinylidene fluoride, polyphenylene ether, crosslinked particles, etc. can also be blended as appropriate.

The thermoplastic resin composition of the present invention can be used as various molded products by injection molding, sheet extrusion, vacuum molding, irregular molding, foam molding, and the like.

Various molded products obtained by the above-mentioned molding method can be used for automobile exteriors, interior parts, various electrical and electronic related parts, housings, etc. by utilizing their excellent performance.

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

Reference Example (6) Polybutylene terephthalate obtained from terephthalic acid dimethyl ester and butanediol manufactured by Sokokoka H and having an intrinsic viscosity (measured at 25° C. using 0-chlorophenol) of 0.83 was used.

Polycarbonate A2200 (weight average molecular weight = 25.900) manufactured by Idemitsu Petrochemical Company Ltd. was used.

(2) Rubber Reinforced Resin (c) -1 manufactured by Shionto Jl.
0 parts, 49 parts of styrene, 21 parts of acrylonitrile, and 130 parts of toluene, stirred at 50°C until the rubber component was completely dissolved, and 0.2 parts of t-dodecylmercaptan,
t-Butylperoxyisopropyl carbonate 0.5
After adding 50% of the solution, a polymerization reaction was carried out at 100° C. for 10 hours. The polymerization product was desolvated by a conventional method and dried, then 0.4 part of 2,2-methylenebis-(4-ethyl-6-t-butylphenol) was added and pelletized using an extruder to form a rubber. A reinforced resin (c)-1 was obtained.

[Rubber reinforced resin (c)-21 In a stainless steel autoclave with an internal volume of 102 and equipped with a ribbon-type stirring blade, the hydride of the conjugated diene polymer described in (c)-6 below was added as a rubber component, which was made into a homogeneous solution in advance. A mixed solution of 30 parts of acrylonitrile, 15 parts of styrene, 120 parts of toluene, and 0.1 part of t-dodecylmercaptan was charged, and the temperature was raised with stirring, and 50 parts of acrylonitrile was added at 50°C.
1 part, 50 parts of methyl methacrylate, 0.5 part of benzoyl peroxide, and 0.1 part of dicumyl peroxide were added, and after the temperature was further raised to 80°C, the stirring rotation speed was increased while controlling the temperature to be constant at 80°C. The polymerization reaction was carried out at 1100 rpm.

After the reaction started, the temperature was raised to 120° C. over 6 to 1 hour, and the reaction was continued for another 2 hours to complete the polymerization. The polymerization conversion rate was 97%.

After cooling this to 100''C, 2.2'methylenebis(4-methyl-6-t-butylphenol)0.
After adding 2 parts, the reaction mixture was taken out from the autoclave, the unreacted monomer and solvent were distilled off by steam distillation, and the mixture was finely pulverized. While substantially distilling off the volatile matter, the polymer was pelletized to obtain rubber reinforced resin (c)-2.

□□□Toyosada Sokooka 1 [Polymer (d)-1) EPM, Mooney viscosity (ML+-=, 100°C) = 7
0, JSREPO7P manufactured by Japan Synthetic Rubber ■ was used.

[Polymer (d)-2) EPDM, Mooney viscosity (M L +.4.100'C
)=88, JSREP57P manufactured by Japan Synthetic Rubber ■ was used.

[Polymer (d) -3) EPDM, Mooney viscosity (ML, , , 100°C)
=105, manufactured by Japan Synthetic Rubber ■, JSREP27 was used.

[Polymer (d)-4) EPDM, Mooney viscosity (ML I, 120°C
)=92, manufactured by Japan Synthetic Rubber ■, JSREP103 was used.

[Polymer (d)-5 (c-D-C block copolymer)]
Polybutadiene hydride (hydrogenated 98%) was used.

[Polymer (d)-6 (A-B-C block copolymer)]
Block A is a styrene block with a molecular weight of 40,000 (styrene content 30%), block B is polybutadiene with a molecular weight of 80,000, and the amount of 1.2-vinyl bonded gold is 52%, block C is polybutadiene with a molecular weight of 10,000, and 1. 2-Hydrogenated block copolymer with a vinyl bond content of 12% (hydrogenation rate 9)
8%) was used.

[Polymer (d)-7 (A-B block copolymer)] Block A is a styrene block, block B is a random copolymer of styrene and butadiene, molecular weight 20
A hydride of a block copolymer (hydrogenation rate of 98%) was used. In addition, the bound styrene content of block A is 10%,
The bound styrene content of block B is 20%.

[Polymer (d)-8) Polybutadiene rubber (manufactured by Japan Synthetic Rubber, JSRBRO
I) was used.

(9) Multi-phase structure thermoplastic resin (e)-13 manufactured by Sotobu ■ 250 parts of distilled water and 0.25 parts of polyvinyl alcohol were added to a stainless steel autoclave, and while stirring, ethylene-glycidyl methacrylate copolymer was added. 70 parts of the compound (glycidyl methacrylate content = 10%) were added and dispersed. As a radical polymerization initiator, 0.15 parts of benzoyl peroxide and as a radical (co)polymerizable organic peroxide, 0.6 parts of t-butylperoxymethacryloyloxyethyl carbonate were dissolved in 21 parts of styrene and 9 parts of acrylonitrile. Added.

Next, the radical polymerization initiator and the radical (
Co) A vinyl monomer containing a polymerizable organic peroxide was impregnated.Then, the temperature was raised to 80-85°C and a polymerization reaction was carried out for 7 hours.

A grafted precursor was obtained by washing with water and drying.

This grafting precursor was extruded using an extruder (200° C.) to carry out a grafting reaction, thereby obtaining a multiphase structure thermoplastic resin (e)-1.

The dispersed particle size of the styrene-acrylonitrile copolymer observed in (e)-1 using a scanning electron microscope was 0.3 to 0.4.
μm, and the grafting rate of styrene polymer to ethylene-glycidyl methacrylate copolymer is 32%.
Met.

[Multiphase structure thermoplastic resin (e)-2 to 4] (Using the components shown in the table below under the manufacturing conditions of eil, (e)-2 to (e)
-4 was obtained.

(Hereinafter, blank spaces) Examples 1 to 22, Comparative Examples 1 to 7 The above components were mixed in the composition ratios shown in Table 1. Pelletization was performed using a co-rotating two-wheel extruder as an extruder. After sufficiently drying the obtained pellets, test pieces for evaluation were obtained using an injection molding machine.

Evaluation: JL method impact resistance; thickness 1/8 according to ASTM D256
#Notched, measured at 23°C.

Heat resistance (heat distortion temperature): Measured according to ASTM D64B at a thickness of 1/4' and a load of 18.5 kg/cj.

Surface appearance of molded product: The appearance of the flat molded plate was visually evaluated according to the following criteria.

◎ = Particularly good O = Good
The test piece was immersed in kerosene under a strain of 1, and after 10 hours, the test piece was evaluated according to the following evaluation criteria.

O = No breakage or microcracks, and good appearance x = Breakage or microcrank occurrence evaluation results are also shown in Table 1.

As is clear from Table 1, the compositions of Examples 1 to 22 are all excellent in heat resistance, impact resistance, chemical resistance, and surface appearance.

On the other hand, in Comparative Example 1, the component (d) was not used, and the impact resistance was poor.

Comparative Example 2 is an example in which the amount of component (a) used is large outside the scope of the present invention, and the impact resistance is poor.

In Comparative Example 3, the amount of component (b) used was large beyond the scope of the present invention, and the chemical resistance was poor.

Comparative Example 4 is a case where the amount of component (c) used is large outside the range of the present invention, and the chemical resistance and heat resistance are poor.

Comparative Example 5 is a case in which the amount of component (d) used is small outside the scope of the present invention, and the molded product has poor surface appearance and poor chemical resistance.

Comparative Example 6 uses ABS, which is outside the scope of the present invention, as component (c).
This is an example using resin, which has poor impact resistance.

Comparative Example 7 is an example in which polybutadiene rubber outside the scope of the present invention was used as component (b), and the impact resistance was poor and the surface appearance was poor.

〔Effect of the invention〕

The thermoplastic resin composition of the present invention has excellent impact resistance, heat resistance, chemical resistance, and surface appearance of molded products, and is suitable for use in automobile exterior and interior parts and electrical and electronic related materials that require high quality. It is possible to provide molded products such as various parts and housing materials, and its industrial utility value is extremely large.

Patent applicant: Japan Synthetic Rubber Co., Ltd. Agent: Patent Attorney Takashi Shirai

Claims (1)

[Claims] (1) (a) Thermoplastic polyester resin 2-96% by weight
, (2) 2 to 96% by weight of aromatic polycarbonate resin,
(c) A vinyl cyanide compound and/or (meth)acrylic acid alkyl ester and an aromatic vinyl compound in the presence of a rubber component mainly composed of a hydrogenated product of an α-olefin copolymer and/or a conjugated diene polymer. Rubber reinforced resin 1 obtained by polymerizing a monomer mixture containing as main components
~80% by weight, and (d) an α-olefin copolymer, a block copolymer mainly composed of an aromatic vinyl compound and a conjugated diene compound,
and 1 to 50% by weight of at least one kind of polymer selected from hydrides of conjugated diene polymers [however, (a) +
(b) + (c) + (d) = 100% by weight].