JPH09221522A - Thermoplastic copolymer and thermoplastic resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic vinyl/vinyl cyanide compound/N-substituted maleimide copolymer having heat resistance, transparency and high mechanical strengths and having a content of residual unreacted N-substituted maleimide of 50ppm or below and to provide a thermoplastic resin composition containing the same. SOLUTION: This copolymer comprises 30-70wt.% units derived from an aromatic vinyl compound, 4-40wt.% units derived from a vinyl cyanide compound and 26-50wt.% units derived from an N-substituted maleimide and has the following properties: the compositional distribution is narrow for every fraction prepared by fractionating the sample on the basis of the molecular weight determined by GPC, it is substantially free from acetone insolubles, the weight- average molecular weight is 100,000-300,000, the number-average molecular weight is 50,000-150,000, and the content of residual unreacted N-substituted maleimide is 50ppm or below. The composition contains the above copolymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel thermoplastic copolymer and a thermoplastic resin composition using the same. More specifically, the present invention is excellent in heat resistance and transparency, and is a thermoplastic terpolymer having high mechanical strength and heat resistance and chemical resistance using the same as a component, and high impact strength. And a thermoplastic resin composition suitable as a material for automobile interior parts and parts for electric / electronic devices.

[0002]

2. Description of the Related Art In recent years, in the fields of automobiles, office machines, electric appliances, etc., it has been attempted to make a part of sheet metal into a resin for the purpose of weight saving, energy saving, and cost reduction. Attempts have been made to replace the alloy of polycarbonate and ABS resin with a heat and impact resistant resin such as modified PPE.

By the way, a styrene-acrylonitrile copolymer (AS resin) is a transparent thermoplastic resin having excellent chemical resistance and high mechanical strength, and has good miscibility with ABS resin and the like. Although it is widely used as a molding material, it has a drawback that it is unsuitable for use at high temperatures due to its poor heat resistance.

As a method for improving the heat resistance of this AS resin, for example, a method of introducing an α-methylstyrene unit and a maleic anhydride unit into the molecular chain is known.
In this method, there is a limit to the improvement of heat resistance, and the obtained resin decomposes at high temperature, resulting in deterioration of quality. Further, in the case of producing a large-sized molded product by the blow molding method, there is a drawback that the above method cannot be adopted because the drawdown caused by the thermal decomposability of the α-methylstyrene is remarkable.

On the other hand, for the purpose of improving such a drawback of the α-methylstyrene, the heat resistance is improved by introducing an N-arylmaleimide unit into the molecular chain of the copolymer of acrylonitrile and styrene. Has been proposed (US Pat. No. 3,652,726, US Pat. No. 3,766,142, Japanese Patent Publication No. 62-5).
No. 0357, Japanese Patent Publication No. 1-34961).

However, the terpolymer of styrene, acrylonitrile, and N-arylmaleimide obtained by these methods has a remarkably wide composition distribution, and therefore has poor physical properties such as heat resistance and mechanical strength and is transparent. It also has the drawback that it is inferior in nature and inevitably subject to restrictions on its use.
Further, the resin composition using such a copolymer has a problem that the effect of improving mechanical strength and heat distortion resistance is not sufficiently exhibited.

On the other hand, as a method for making the composition distribution of the ternary copolymer uniform, it is known that it is preferable to carry out the copolymerization by a continuous solution polymerization method. A method for producing the terpolymer by the continuous solution polymerization method is disclosed in Japanese Patent Laid-Open No. Sho 6-62
Although described in JP-A 1-276807, in this method, the composition distribution of the copolymer becomes uniform,
A copolymer having high heat resistance and little residual phenylmaleimide cannot be obtained. That is, when a large amount of phenylmaleimide is supplied to the polymerization tank in order to increase the heat resistance, a side reaction occurs when the reaction liquid containing a large amount of maleimide is processed by the devolatilization device, and therefore a considerable amount. This results in an undesirable situation in which the amount of residual phenylmaleimide in the copolymer is increased due to the formation of the oligomer. As described above, in the prior art, when the devolatilization device was operated under conditions of high temperature and high vacuum in order to reduce residual phenylmaleimide, a large amount of oligomer was generated and the composition distribution of the copolymer was unsatisfactory. Homogenization and pyrolysis,
This produces heat coloring.

It is important that the residual amount of unreacted N-arylmaleimide in the terpolymer is 50 ppm or less. If this amount exceeds 50 ppm, for example, when the terpolymer is used in a molded product that comes into contact with food, it may elute into the food and cause safety and health problems.
There are problems such as remarkable coloring and mesiness during molding, and deterioration of heat resistance, which inevitably limits the applications. Further, in the prior art, when the heat resistance of the terpolymer was improved and the residual amount of N-arylmaleimide was reduced, the composition distribution of the copolymer tended to be broadened.

[0009]

Under the above circumstances, the present invention has an unreacted N-substituted maleimide residual amount of 5 which has heat resistance and transparency and high mechanical strength.
A thermoplastic copolymer of 0 ppm or less of an aromatic vinyl compound, a vinyl cyanide compound and an N-substituted maleimide, and a molded article containing the copolymer, which has excellent heat resistance and chemical resistance and high impact strength. The purpose of the present invention is to provide a thermoplastic resin composition capable of giving

[0010]

As a result of intensive studies to achieve the above object, the present inventors have found that aromatic vinyl compounds, vinyl cyanide compounds, and N-substituted maleimides in a specific ratio are used alone. By copolymerizing the monomer mixture by a continuous solution polymerization method, the composition distribution is narrow and unreacted N-
The residual amount of the substituted maleimide is 50 ppm or less, which is excellent in heat resistance and transparency, and a thermoplastic terpolymer having high mechanical strength is obtained, and the terpolymer has a specific thermoplastic copolymer weight. Thermoplastic resin composition in which the coalesced is blended in a predetermined ratio, glass fiber or glass flakes in the above terpolymer or composition, or a thermoplastic resin composition in which a polycarbonate resin is blended in a predetermined ratio is heat resistant. ,
It was found that a molded product having excellent chemical resistance and high rigidity and impact strength can be provided, and the present invention has been completed based on this finding.

That is, the present invention comprises (a) aromatic vinyl compound unit 30 to 70% by weight, (b) vinyl cyanide compound unit 4 to 40% by weight, and (c) N-substituted maleimide 26 to 50% by weight. A copolymer having a narrow distribution of copolymer composition measured by GPC for each molecular weight classification, containing virtually no acetone insoluble matter, and having a weight average molecular weight of 100,000 to 300,000 and a number average molecular weight of 5 10,000 to 150,000,
The residual amount of unreacted substituted maleimide is 50 ppm or less, thermoplastic copolymer (I), (A) thermoplastic copolymer (I) 30 to 70% by weight, and (B) (D)
Thermoplastic copolymer (II) 7 having a weight average molecular weight of 80,000 to 300,000 consisting of 50 to 80% by weight of an aromatic vinyl compound unit and 50 to 20% by weight of a (c) vinyl cyanide compound unit.
A thermoplastic resin composition containing 0 to 30% by weight,
(A) 30 to 70% by weight of the thermoplastic copolymer (I),
(B) 5 to 30% by weight of the thermoplastic copolymer (II),
(C) A monomer mixture of an aromatic vinyl compound and a vinyl cyanide compound is obtained in at least one rubber component selected from acrylate rubber and diene rubber having Tg of 25 ° C. or less. The ratio of each unit in the polymer is in the range of 50:50 to 80:20 in weight ratio, and the thermoplastic graft copolymer obtained by graft polymerization so that the content of the rubber component is 30 to 60% by weight. Thermoplastic resin composition containing 25 to 45% by weight of polymer (III), (A) thermoplastic copolymer (I) 30 to
70% by weight, and (B) thermoplastic copolymer (II) 5 to 3
0% by weight, and (D) at least one rubber component selected from an acrylate rubber and a diene rubber having a Tg of 25 ° C. or less, an aromatic vinyl compound, a vinyl cyanide compound, and N-phenylmaleimide. Wherein the ratio of the aromatic vinyl compound unit and the vinyl cyanide compound unit in the resulting copolymer is in the range of 50:50 to 80:20 by weight, and the N-phenylmaleimide unit is Content of 5 to 10% by weight, and a thermoplastic graft copolymer (IV) obtained by graft polymerization so that the content of the rubber component becomes 30 to 60% by weight. A thermoplastic resin composition comprising (A) a thermoplastic copolymer (I) in an amount of 30 to 70% by weight, and (E) (a) a hard resin particle having an acrylic ester cross-linked polymer layer on the surface thereof. Particles and heavy It weight ratio of the body layer is not five ninety-five 4
Rubber-like copolymer particles 3 provided so as to be 0:60
0 to 80% by weight, and (b) 20 to 80% by weight of an acrylic acid ester unit and 5 units of an aromatic vinyl compound, which are sequentially formed on the surface of the rubbery copolymer particles by graft polymerization.
To 50% by weight and vinyl cyanide compound unit 5 to 50% by weight, and a rubber-like elastic layer 10 to 30% by weight and (c) aromatic vinyl compound unit 30 to 90% by weight and vinyl cyanide compound unit 10 to 10% by weight. Multilayer graft copolymer particles having an average particle size of 0.2 to 0.8 μm, comprising 10 to 40% by weight of a resin layer consisting of 50% by weight and optionally 20% by weight or less of acrylic acid ester units ( V) a thermoplastic resin composition comprising 25 to 45% by weight and optionally (B) a thermoplastic copolymer (II) of 50% by weight or less, and the thermoplastic copolymer (I) Alternatively, a thermoplastic resin composition obtained by blending (F) a polycarbonate resin in a weight ratio of 1/9 to 9/1 with respect to each of the above compositions, or (G) a glass fiber or a glass flake is selected. At least one inorganic filler has is to provide a thermoplastic resin composition obtained by blending in a range of weight ratio of 1 / 9-4 / 6.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The characteristic feature of the copolymer (I) of the present invention is that the composition distribution is extremely narrow. For example, when the copolymer is dissolved in tetrahydrofuran and the molecular weight is divided by GPC, the copolymer according to the prior art has a different composition depending on each molecular weight and exhibits an extremely wide composition distribution. It can be said that (I) has a uniform composition according to each molecular weight, and has a very narrow composition distribution for each molecular weight category, and is substantially constant. As described above, since the copolymer (I) of the present invention has a uniform composition distribution, it is excellent in transparency and heat distortion resistance and has high mechanical strength.

Examples of the monomer for forming the unit (a) in the copolymer (I) of the present invention, that is, the aromatic vinyl compound unit include styrene, α-methylstyrene, o-
Methyl styrene, m-methyl styrene, p-methyl styrene, t-butyl styrene, chlorostyrene and the like can be mentioned, and among them, styrene is preferable. These aromatic vinyl compounds may be used alone or in combination of two or more.

Examples of the monomer forming the (b) unit in the copolymer (I) of the present invention, that is, the vinyl cyanide compound unit include acrylonitrile and methacrylonitrile. Among them, acrylonitrile is preferable. It is suitable. The vinyl cyanide compound may be used alone or in combination of two or more.

The (C) unit in the copolymer (I) of the present invention, that is, the N-substituted maleimide unit has the general formula

Embedded image (Wherein R is an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group), and the monomer forming this unit is, for example, N-methylmaleimide, N-ethylmaleimide, N
-Butylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-chlorophenylmaleimide, etc., among which N-phenylmaleimide is particularly preferred from the viewpoints of heat resistance improvement, easy availability, economical efficiency, etc. Is. These N-substituted maleimides may be used alone or in combination of two or more.

Regarding the content ratio of each unit in the copolymer (I) of the present invention, the aromatic vinyl compound unit is 30 to 7
0% by weight, vinyl cyanide compound unit 4 to 40% by weight
And 26 to 50% by weight of N-substituted maleimide units, preferably 35 to 60% by weight of aromatic vinyl compound units, 10 to 30% by weight of vinyl cyanide compound units and 26 to 40% by weight of N-substituted maleimide units. It is necessary to contain it in the ratio of.

When the content of the aromatic vinyl compound unit is less than 30% by weight, the mechanical strength is low, and when it exceeds 70% by weight, the heat resistance is lowered. Further, if the content of the vinyl cyanide compound unit is less than 4% by weight, the mechanical strength is low,
If the content is more than wt%, the heat resistance tends to be low and heat coloring tends to occur. Further, if the content of the N-substituted maleimide unit is less than 26% by weight, the effect of improving the heat resistance is not sufficiently exhibited, and if it exceeds 50% by weight, the mechanical strength and fluidity are deteriorated.

The copolymer (I) of the present invention is required to have a weight average molecular weight of 100,000 to 300,000 and a number average molecular weight of 50,000 to 150,000, and the weight average molecular weight and the number average molecular weight are within the above ranges. If it deviates from the above range, the object of the present invention cannot be sufficiently achieved.
Further, the copolymer of the present invention is required to contain substantially no acetone insoluble matter. The acetone insoluble matter means an insoluble matter when 3 g of the copolymer is dissolved in 27 g of acetone at a temperature of 25 ° C. When an alternating copolymer of an aromatic vinyl compound and an N-substituted maleimide in a molar ratio of about 1: 1 is dissolved in acetone under the above conditions, the insoluble content is about 99% by weight. Therefore, the fact that the copolymer of the present invention is substantially free of the acetone-insoluble matter means that it is substantially free of the alternating copolymer. The copolymer containing the alternating copolymer is unfavorable because it has poor balance between heat resistance and mechanical strength.

Further, the copolymer (I) of the present invention must have a residual amount of unreacted N-substituted maleimide of 50 ppm or less. When the residual amount of the N-substituted maleimide exceeds 50 ppm, the heat distortion temperature tends to decrease, and the use as a food packaging material is limited, which is not preferable.

The copolymer (I) can be produced, for example, by using a continuous solution polymerization method. Regarding the usage ratio of each monomer in this case, the aromatic vinyl compound is 30 to
90% by weight, vinyl cyanide compound 4 to 40% by weight, N
The proportion of the substituted maleimide is 5 to 50% by weight, preferably the aromatic vinyl compound is 40 to 80% by weight, the vinyl cyanide compound is 10 to 30% by weight, and the N-substituted maleimide is 10 to 40% by weight.

As the solvent, for example, aromatic hydrocarbons, ketones, alcohols, ethers and the like can be used, but preferable solvents include ethylbenzene, toluene, xylene, methyl ethyl ketone, butanol, tetrahydrofuran and the like. You can These solvents may be used singly or as a mixture of two or more.

The radical initiator used in the polymerization is not particularly limited, and those which have been conventionally used in the production of AS resins, for example, a 10-hour half-life of 70 to 1 are used.
It is possible to use an organic peroxide or an azo compound having a temperature of 20 ° C. Examples of such a material include t-butylperoxyisopropyl carbonate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and azoisobutyronitrile.

Further, at the time of polymerization, known molecular weight regulators, plasticizers, heat stabilizers, antioxidants, light stabilizers and the like may be added, if desired. As the polymerization apparatus used for producing the copolymer (I), it is desirable to use a complete mixing type reactor and a laminar flow reactor arranged in series. A desired copolymer can be continuously produced by continuously supplying a required amount of each monomer, solvent, radical initiator and the like to this apparatus.

The polymerization rate in the completely mixed reactor is 3
It is 0% by weight or more, preferably 40% by weight or more, more preferably 50 to 65% by weight, and the composition of the unreacted monomer in the reaction liquid flowing out from the complete mixing type reactor is Based on the total amount of the body, the aromatic vinyl compound is 30 ~
It is desirable that 80% by weight, the vinyl cyanide compound is 10 to 50% by weight, and the N-substituted maleimide is 20% by weight or less, preferably 15% by weight or less.

Further, the polymerization rate in the final laminar flow reactor is 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more. The difference from the polymerization rate in the laminar flow reactor is preferably 10% by weight or more.

The temperature in this polymerization reaction is usually 70 to 1
It is selected in the range of 80 ° C., but 70 to 160 ° C. in the complete mixing type reactor and 90 to 180 in the laminar flow reactor.
C., preferably 90 to 140.degree. C. for the former and 100 for the latter.
It is desirable to be in the range of to 160 ° C. The residence time (reactor volume / feed liquid amount) in the laminar flow reactor is usually 0.5 hour or longer, preferably 1 hour or longer.

When the polymerization rate in the complete mixing type reactor is less than 30% by weight, the aromatic vinyl compound and the N-substituted maleimide are likely to form an alternating copolymer having a molar ratio of about 1: 1. When the content of the unreacted N-substituted maleimide in the reaction liquid flowing out from the mixed reactor exceeds 20% by weight based on the total amount of the unreacted monomers, the aromatic vinyl compound and N -With a substituted maleimide, it becomes easy to form an alternating copolymer having a molar ratio close to 1: 1,
Not preferred.

The polymerization rate in the final laminar flow reactor is 5
If it is less than 0% by weight, the content of unreacted N-substituted maleimide in the obtained copolymer may exceed 50 ppm. A polymer containing an alternating copolymer in which the molar ratio of the aromatic vinyl compound and the N-substituted maleimide is about 1: 1 is not preferable because the heat resistance and the mechanical strength are poorly balanced. Regarding the determination of whether or not such an alternating copolymer is present in the polymer, when 3 g of the alternating copolymer is dissolved in 27 g of acetone, approximately 99% by weight is insoluble in acetone. If the copolymer is substantially free of acetone insolubles, it means substantially free of alternating copolymers,
This can be determined.

Furthermore, the content of unreacted N-substituted maleimide in the copolymer must be 50 ppm or less. The content of this unreacted N-substituted maleimide is 50 p
If it exceeds pm, the heat distortion temperature tends to decrease, and heat coloring tends to occur, which inevitably limits the use as a food packaging material.

The complete mixing type reactor used in the present invention is not limited to the reactor of the specified type, but the polymerization product, the composition of the polymerization liquid and the temperature are equal in each part of the reaction vessel. Those that are retained are preferred. Further, the laminar flow reactor is not limited to the reactor of the specified type, but a reactor in which the polymerization proceeds in an integrated manner is preferable.

The number of reactors is not particularly limited, but one or two complete mixing type reactors and one to three laminar flow reactors are preferable. Furthermore, in a laminar flow reactor,
The aromatic vinyl compound may be added in an amount of 20% by weight or less, preferably 15% by weight or less of the intended amount. In particular, when the unreacted vinyl cyanide compound is present in the reaction liquid supplied to the laminar flow reactor in an amount of 30% by weight or more based on the amount used, the addition is carried out to obtain a copolymer in the resulting copolymer. Advantageously, the content of unreacted N-substituted maleimide can be below 50 ppm.

The polymerization solution thus obtained is usually introduced into a volatile matter separating and removing apparatus to remove unreacted monomers and solvent, and then, if necessary, a hindered phenolic antioxidant or a hindered amine. System, benzotriazole type weathering agent, etc. are added, and the polymer in a molten state is extruded, cooled, solidified, and shredded to obtain the copolymer (I) of the present invention.
Is continuously obtained. In the volatile matter separation / removal device, the volatile matter is removed by allowing the volatile matter to stay for about 5 to 160 minutes under the conditions of a normal temperature of 200 to 270 ° C. and a vacuum degree of 0.1 to 50 Torr.

The thermoplastic resin composition of the present invention comprises (A) the thermoplastic copolymer (I), (B) (d) 50 to 80% by weight of an aromatic vinyl compound unit, and (v) vinyl cyanide. A thermoplastic copolymer (II) comprising 50 to 20% by weight of a compound unit, wherein the copolymer (I
Examples of the monomer forming the aromatic vinyl compound unit in I) include styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene and the like, among which styrene is preferable. .
One of these aromatic vinyl compounds may be used, or 2
It may be used in combination of more than one kind. Further, as the monomer forming the vinyl cyanide compound unit, for example, acrylonitrile, methacrylonitrile and the like are used, and of these, acrylonitrile is preferable. This vinyl cyanide compound may be used alone or in combination of two or more kinds.

The content ratio of the aromatic vinyl compound unit and the vinyl cyanide compound unit in the thermoplastic copolymer (II) is appropriately in the range of 50:50 to 80:20 by weight. The weight average molecular weight of this copolymer (II) is required to be in the range of 80,000 to 300,000. If the weight average molecular weight deviates from the above range, the object of the present invention cannot be sufficiently achieved.

In order to produce this copolymer (II), a radical polymerization method such as a continuous bulk polymerization method, a continuous solution polymerization method, an emulsion polymerization method or a suspension polymerization method can be used. Is preferred. As the solvent used in this continuous solution polymerization, for example, toluene, ethylbenzene,
Hydrocarbon solvent such as xylene, methyl ethyl ketone,
Examples include polar solvents such as butyl alcohol and tetrahydrofuran, and among these, hydrocarbon solvents are preferable.

Next, an example of producing the thermoplastic copolymer (II) by a continuous solution polymerization method will be described. First, a monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in predetermined proportions, respectively. In addition, solvents used as desired, radical polymerization initiators such as organic peroxides and organic azo compounds, chain transfer agents such as alkyl mercaptans and α-methylstyrene dimers, and weathering agents such as hindered amines and benzotriazoles. , And after uniformly dissolving each by adding a predetermined amount, the solution is continuously supplied to the polymerization vessel to polymerize, then continuously take out the polymer solution and supply it to a high temperature depressurized container to supply the unreacted monomer. And after distilling off the solvent, an antioxidant and a weathering agent are added if necessary, and then the polymer in a molten state is extruded, cooled, solidified and shredded. Thermoplastic copolymer of interest (II)
Get.

In this method, the polymerization temperature is usually 10
The temperature, the degree of vacuum, and the residence time in the high-temperature decompression container at 0 to 160 ° C. are selected in the ranges of 200 to 270 ° C., 1 to 50 Torr, and 5 to 160 minutes, respectively. In the thermoplastic resin composition, the thermoplastic copolymer (I) as the component (A) and the thermoplastic copolymer (II) as the component (B) are
It is used in the range of 30 to 70% by weight and 70 to 30% by weight, respectively. When the content ratio of the copolymers (I) and (II) is within the above range, a composition having excellent heat resistance and fluidity can be obtained.

In the present invention, in order to further improve the impact resistance in some cases, the thermoplastic copolymer (I) and the thermoplastic copolymer (I) as the component (B) are used.
Along with I), the thermoplastic graft copolymer (III) may be contained as the component (C), or the thermoplastic graft copolymer (IV) may be contained as the component (D). The thermoplastic graft copolymer (III) as the component (C) is obtained by graft-polymerizing a monomer mixture of an aromatic vinyl compound and a vinyl cyanide compound onto an acrylate rubber or a diene rubber having a Tg of 25 ° C. or lower. Further, the thermoplastic graft copolymer (IV) as the component (D) is obtained by adding an aromatic vinyl compound, a vinyl cyanide compound and N to an acrylate rubber or a diene rubber having a Tg of 25 ° C. or less. It is obtained by graft polymerizing a monomer mixture with -phenylmaleimide.

Examples of the acrylate rubber having a Tg of 25 ° C. or lower include, for example, a polymer containing a butyl acrylate unit or a 2-ethylhexyl acrylate unit as a main constituent unit, while a diene rubber having a Tg of 25 ° C. or lower. Examples thereof include polybutadiene and polyisoprene. These rubbers may be used alone or in combination of two or more.

Examples of the monomeric aromatic vinyl compound to be graft-copolymerized with these acrylate-based or diene-based rubbers include styrene, α-methylstyrene, vinyltoluene, t-butylstyrene and chlorostyrene. Of these, styrene is preferred. These aromatic vinyl compounds may be used alone or in combination of two or more. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Of these, acrylonitrile is preferable. The vinyl cyanide compound may be used alone or in combination of two or more kinds. The ratio of aromatic vinyl compound to vinyl cyanide compound used is such that the weight ratio of aromatic vinyl compound unit to vinyl cyanide compound unit in the resin obtained by graft polymerization is 50:50 to 80:20. Used in proportion.

The graft copolymers (III) and (I
The content of the rubber component in V) needs to be in the range of 30 to 60% by weight. Further, the graft copolymer (III) preferably contains the α-methylstyrene unit in a proportion of 10 to 30% by weight. Further, the content of N-phenylmaleimide unit in the graft copolymer (IV) is selected in the range of 5 to 10% by weight. Thus, by introducing α-methylstyrene unit or N-phenylmaleimide unit into the graft copolymer, the Tg of the graft layer is increased, and the fading property of the injection molded product, which is a drawback of the prior art, is significantly increased. To be improved. Therefore, in the case of the composition of the present invention, the injection-molded article does not fade even in a heat environment of 110 ° C., and there is no problem in practical use.

The graft copolymers (III) and (I
The method for producing V) is not particularly limited, and any method conventionally used when producing an ABS resin by conventional graft polymerization, such as emulsion polymerization, bulk polymerization, bulk suspension polymerization, is selected. A method can be selected and used.

In the thermoplastic resin composition of the present invention, the graft copolymer (III) or (D) of the component (C) is used.
When the graft copolymer (IV) as a component is used, the blending ratio of each component is 30 to 70% by weight of the thermoplastic copolymer (I) as the component (A) and the thermoplastic copolymer as the component (B). 5 to 30% by weight of the compound (II) and 25 to 45% by weight of the thermoplastic graft copolymer (III) of the component (C) or the thermoplastic graft copolymer (IV) of the component (D). It is necessary to blend. If the content of each component deviates from the above range, the object of the present invention cannot be sufficiently achieved.
In particular, when the content of the component (C) or the component (D) is within the above range, a composition having good heat resistance and fluidity can be obtained.

Further, the thermoplastic copolymer (I) of the component (A) (30 to 70% by weight), the multilayer graft copolymer particle (V) (E) of 25 to 45% by weight, and optionally the above-mentioned The present invention also includes a thermoplastic resin composition containing 50% by weight or less of the component (B) thermoplastic copolymer (II).

The multi-layered graft copolymer particles (V) are
(A) Rubber-like copolymer particles formed by providing an acrylic acid ester-based cross-linked polymer layer (second layer) on the surface of hard resin particles (first layer), and sequentially on the surface of the rubber-like copolymer particles. (B) Rubber-like elastic material layer (third part) provided by graft polymerization
Layer) and (c) resin layer (fourth layer), and each layer has an important function.

First, the innermost hard resin layer (first layer) is
It is important not only to increase the elastic modulus of the rubbery copolymer but also to determine the final particle size of the multilayer graft copolymer in seed polymerization. The content ratio of the hard resin layer of the first layer to the acrylic ester crosslinked polymer layer of the second layer in the rubber-like copolymer particles composed of the first layer and the second layer is 5:95 by weight. To 40:60. If the content of the hard resin layer is less than the above range, the effect of increasing the elastic modulus is not sufficient, and if it is more than the above range, the elastic modulus of the rubber-like copolymer increases too much and the impact strength decreases. The hard resin is not particularly limited as long as it can be obtained by a usual emulsion polymerization method. For example, alkyl methacrylate such as methyl methacrylate, ethyl methacrylate and propyl methacrylate; aromatic vinyl compounds such as styrene and α-methylstyrene; high glass transition points such as vinyl cyanide compounds such as acrylonitrile and methacrylonitrile ( The monomer which gives the polymer of Tg) is mentioned. These monomers may be used alone or in combination of two or more, and may be, for example, methyl acrylate, ethyl acrylate, propyl acrylate, to the extent that the Tg of the obtained polymer is not lowered. It may be used in combination with a monomer that gives a low Tg polymer such as butyl acrylate.

On the other hand, the acrylic acid ester-based crosslinked polymer layer of the second layer is a layer provided for imparting impact strength, and as the acrylic acid ester, butyl acrylate,
Examples thereof include alkyl acrylates having an alkyl group having 1 to 10 carbon atoms such as ethyl acrylate and 2-ethylhexyl acrylate, aromatic acrylates such as benzyl acrylate, and the like. These acrylic acid esters may be used alone or in combination of two or more, and if desired, other copolymerizable vinyl monomers such as styrene, acrylonitrile, methacrylonitrile and methyl methacrylate. , Methacrylic acid, acrylic acid, etc. may be used in combination. The cross-linking agent used in the acrylic acid ester-based cross-linked polymer is a cross-linkable monomer having at least two C = C bonds in the molecule, and can be copolymerized with the acrylic acid ester. Examples thereof include unsaturated acid esters of polyols such as ethylene glycol dimethacrylate; unsaturated alcohol esters of polybasic acids such as triallyl cyanurate and triallyl isocyanurate; and divinyl compounds such as divinylbenzene.
The content of the rubber-like copolymer particles (first layer, second layer) in the multilayer graft copolymer particles (V) is 30 to 8.
It must be in the range of 0% by weight. If this amount deviates from the above range, the effect of imparting impact strength will not be sufficiently exerted.

The third layer composed of the rubber-like elastic material layer comprises the rubber-like polymer particles composed of the first layer and the second layer and the fourth layer.
It is an intermediate layer provided between the resin layer and the resin layer, and has the function of improving the adhesiveness between the rubbery copolymer and the fourth layer. The third rubber-like elastic layer is composed of 20 to 80% by weight of acrylic acid ester units and 5 to 5 units of aromatic vinyl compounds.
75% by weight and vinyl cyanide compound unit 5 to 50% by weight
It is necessary to include and. If the content of acrylic acid ester units is less than 20% by weight, the adhesiveness to the acrylic acid ester-based crosslinked polymer layer of the second layer is poor and the impact strength is insufficient, and if it exceeds 80% by weight, the fourth layer Adhesiveness with the resin layer is deteriorated and impact strength is lowered.

The rubber-like elastic material layer is a rubber composed of a monomer mixture of an acrylic ester, an aromatic vinyl compound, a vinyl cyanide compound and a crosslinking agent, and the first layer and the second layer. It can be formed by graft-polymerizing the linear copolymer particles. At this time, as the acrylate ester, those exemplified in the description of the acrylic acid ester-based crosslinked polymer layer of the second layer can be used. This acrylic ester may be used alone,
Two or more kinds may be used in combination. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, halogenated styrene, etc. These may be used alone or in combination of two or more. May be. Further, examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, which may be used alone or in combination of two or more kinds.

On the other hand, as the cross-linking agent, those exemplified in the description of the second layer can be used, and the amount thereof is usually in the range of 0.05 to 5% by weight based on the weight of the monomer mixture. Is selected in. Further, the content of the third layer in the multilayer graft copolymer particles (V) needs to be in the range of 10 to 30% by weight. The resin layer of the fourth layer in the multi-layered graft copolymer particles is a layer provided to improve compatibility with the thermoplastic copolymer (I) as the component (A), and is an aromatic vinyl. Compound unit 30-90
It is necessary to contain 10% to 50% by weight of vinyl cyanide compound units and 20% by weight or less of acrylic acid ester units optionally introduced. If the content of the acrylic acid ester unit exceeds 20% by weight, the compatibility with the thermoplastic copolymer (I) as the component (A) becomes poor and the impact strength decreases.

The resin layer of the fourth layer was provided with a monomer mixture of an aromatic vinyl compound, a vinyl cyanide compound and optionally used acrylate, and a rubber-like elastic layer of the third layer. It can be formed by graft-polymerizing the rubbery copolymer particles. At this time, as the aromatic vinyl compound and the vinyl cyanide compound, those exemplified in the description of the rubber-like elastic layer of the third layer can be used, and as the acrylate ester, the one of the second layer can be used. What was illustrated in the description of the acrylic acid ester type crosslinked polymer layer can be used. Each of these monomers may be used alone or in combination of two or more. Further, the content of this fourth layer in the multilayer graft copolymer particles (V) is 10 to 4
It must be in the range of 0% by weight.

The average particle size of the multi-layer graft copolymer particles (V) of the component (E) in the composition of the present invention is 0.2.
It is necessary to be in the range of 0.8 μm. When the average particle size is less than 0.2 μm, the resulting molded article has excellent surface gloss but low impact strength, and 0.8 μm.
If it exceeds, the impact strength is high, but the surface gloss is poor.

As a method for producing the multi-layered graft copolymer particles, an emulsion polymerization method in which a monomer is polymerized in the presence of an emulsifier, a polymerization initiator and a chain transfer agent, particularly, in the presence of a hard resin as an innermost layer, A seed polymerization method or the like in which a monomer is polymerized under conditions that suppress the generation is preferably used. Examples of the emulsifier include carboxylic acids having 2 to 22 carbon atoms; anionic emulsifiers such as alcohols having 6 to 22 carbon atoms or sulfonates of alkylphenols; nonionic emulsifiers obtained by adding an alkylene oxide to an aliphatic amine or amide; Examples thereof include cationic emulsifiers such as compounds containing a graded ammonium salt. Examples of the polymerization initiator include water-soluble peroxides such as hydrogen peroxide and alkali metal salts and ammonium salts of persulfate; oil-soluble organic peroxides such as benzoyl peroxide and cumene hydroperoxide; azobisisobutyro An azo compound such as nitrile is used alone or in combination. Further, as a redox catalyst, a mixture of a reducing agent and a peroxide, for example, a reducing agent such as hydrazine, bissulfite, thiosulfite, an alkali metal salt of hydrosulfite, or a soluble oxidizable sulfoxyl compound, and the peroxide. A mixture with a substance can be used. Furthermore, examples of the chain transfer agent include alkyl mercaptans such as t-dodecyl mercaptan, toluene, xylene, chloroform, and halogenated hydrocarbons.

Regarding the method of adding the monomers, they may be added all at once, but it is advantageous to add them in several times or continuously. In this case, the polymerization reaction can be easily suppressed, and overheating and solidification can be prevented. Further, in order to form the rubber-like elastic body layer of the third layer and the resin layer of the fourth layer, after completing the polymerization reaction for forming the acrylic acid ester-based crosslinked polymer layer of the second layer, The monomer for forming elastic elastomer layer and the monomer for forming resin layer may be added and sequentially polymerized, or unreacted monomer may be added without completing the polymerization reaction for forming the acrylic ester crosslinked polymer layer. An aromatic vinyl compound and a vinyl cyanide compound may be added to the rubber-like elastic body layer and the resin layer in the state of remaining.

Further, as a method of suppressing the particle diameter of the multilayer graft copolymer particles, a part of the latex (seed latex) obtained by the polymerization of the hard resin layer of the innermost layer is taken out, and ion-exchanged water, an emulsifier, When the monomer is added and the seed polymerization is continued, a method of controlling the particle diameter of the multilayer graft copolymer particles by adjusting the amount of the seed latex taken out and suppressing the number of particles of the seed latex can be used. .

The thus obtained multi-layered graft copolymer particles are used as the component (E), and the above-mentioned thermoplastic copolymer (I) is added as the component (A) to the component (B). By blending the thermoplastic copolymer (II) as a component, a thermoplastic resin composition having excellent heat resistance, chemical resistance, weather resistance, impact resistance, fluidity and appearance can be obtained. The content of each component in this composition is
Component (A) is 30 to 70% by weight, component (E) is 25 to 4
It is necessary that the content of the component (B) is 5% by weight, and optionally 50% or less. When the content of the component (A) is less than 30% by weight, heat resistance is insufficient, and when it exceeds 70% by weight, impact resistance and fluidity are deteriorated. Also,
If the content of the component (E) is less than 25% by weight, the effect of improving impact resistance is not sufficiently exerted, and if it exceeds 45% by weight, the rigidity and heat resistance decrease. On the other hand, if the content of the component (B) exceeds 50% by weight, the heat resistance will decrease.

In the present invention, the thermoplastic copolymer (I) used as the component (A) in each composition must have a uniform composition distribution in order to sufficiently achieve the object. . This composition distribution can be obtained as follows. That is, about 100 mg of the copolymer is precisely weighed, placed in a 10 ml measuring flask, and dissolved in tetrahydrofuran (THF) to a constant volume. This 100 μl
Is injected into a GPC device and the molecular weight distribution is measured. on the other hand,
In the measurement of molecular weight distribution, if a peak begins to appear on the chart, it is sampled every 1 minute of outflow time,
After adding a certain amount of KBr powder to this, THF is evaporated and infrared absorption is measured by the diffuse reflection method. The composition ratio of each fraction was CN group (2237 cm ⁻¹ ), C
= O group (1712 cm ⁻¹ ), benzene ring (760 cm
The absorption intensity of ( ^-1 ) can be measured and determined using a calibration curve prepared in advance.

Regarding the definition of the narrowness (uniformity) of the composition distribution, the average composition of styrene units is X1 and the composition is X, the average composition of the acrylonitrile unit is Y1, the composition is Y, the average composition of the N-phenylmaleimide unit is Z1, and the composition is Z. X = (1 ± 0.20) X1 (wt%) Y = (1 ± 0.20) Y1 (wt%) Z = (1 ± 0.20) Z1 (wt%) X + Y + Z = 100 It can be said that the composition distribution is narrow and uniform.

That is, the copolymer (I) in the present invention
The compositional distribution of the copolymer must have a deviation from the average value within 20%, and if it exceeds 20%, the copolymer (I)
Has a reduced transparency, causes turbidity, and a reduced mechanical strength, which is not preferable because it limits industrial applications.

The thermoplastic copolymer (I) and each composition of the present invention contain (G) in order to improve heat resistance and rigidity.
At least one inorganic filler selected from glass fibers and glass flakes can be blended as a component. Since the copolymer (I) and the composition have a maleimide group or a cyano group, the addition of glass fibers or glass flakes effectively improves heat resistance and rigidity. The glass fiber preferably has an aspect ratio (L / D) of 20 or more and a fiber diameter of 5 to 15 μm in the composition, and the glass flake has a thickness of 1 to 1 in the composition. It is desirable that the length is in the range of 10 μm and the length is in the range of 10 to 500 μm. If the shape of the glass fiber or glass flake deviates from the above range, the object of the present invention cannot be sufficiently achieved.

These glass fibers and glass flakes may be used alone or in combination. These glass fibers and glass flakes may be used as they are, but it is preferable to use those which have been previously treated with a surface treatment agent such as a coupling agent, or those which have been previously subjected to a focusing treatment with a resin.

Examples of the surface treatment agent include silane-based agents,
Examples thereof include titanate-based, aluminum-based, chromium-based, zirconium-based, borane-based coupling agents, and among these, silane-based coupling agents and titanate-based coupling agents are preferable, and silane-based coupling agents are particularly preferable. is there.

Further, the type of glass is not particularly limited, and any of alkali-containing glass, low-alkali glass and non-alkali glass may be used. Further, as the glass fiber, for example, any of roving, chopped strand, milled fiber and the like can be used.

When glass fiber is used as the inorganic filler (G) in the composition of the present invention, it is desirable that the resin be subjected to a bundling treatment with an appropriate resin, which resin is compatible with the resin of the above-mentioned resin component. A polymer latex,
For example, a copolymer latex composed of aromatic vinyl compound units and vinyl cyanide compound units is usually used. The method of this focusing treatment is not particularly limited, and a conventionally used method, for example, 100 to 5 is used.
A method may be used in which the latex is applied to glass fibers composed of about 10,000 filaments by a method such as dip coating, roller coating, spray coating, flow coating or spray coating, and then dried.

In the present invention, the glass fibers and glass flakes need to be blended in a weight ratio of 1/9 to 4/6 with respect to each composition of the thermoplastic copolymer (I). is there. If the content is less than the above range, the heat resistance and mechanical properties will be insufficient, and if it is more than the range, kneading will be difficult and the moldability will be deteriorated.

Further, the thermoplastic copolymer (I) of the present invention
And, a polycarbonate resin can be added to each composition in the range of 1/9 to 9/1 with respect to the resin component.
As the polycarbonate resin, for example, a dihydroxydiarylalkane-based polycarbonate such as a polycarbonate prepared from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) as a raw material is suitable.

The composition of the present invention may optionally contain various additives such as calcium carbonate, calcium sulfate, barium sulfate, aluminum hydroxide, talc, clay, mica, silica, as long as the object of the present invention is not impaired. Inorganic fillers such as diatomaceous earth, montmorillonite, bentonite, zinc borate, barium metaborate, or antioxidants such as hindered phenols and phosphites,
Light resistance agents such as hindered amines, and additives such as flame retardants, antistatic agents and colorants can be added.

The method for preparing the thermoplastic resin composition of the present invention is not particularly limited. For example, each resin component is mixed with a V-blender, a ribbon blender, a Henschel mixer, a tumbler blender, or after mixing, for example, Banbury. You may melt-knead with a mixer, a kneader, an oven roll, various extruders, etc., and then pelletize.

When glass fibers or glass flakes are used, the strands obtained by extrusion coating the glass fiber rovings bundled as described above with a resin component using an extruder are cut. It may be pelletized, or chopped strands by cutting the strands of the glass fiber subjected to the bundling treatment into an appropriate size, or short glass fibers or glass flakes and resin components are mixed using the above mixer, or Alternatively, after mixing, they may be melt-kneaded using the above-mentioned kneader and then pelletized. The composition of the present invention thus obtained can be molded into a desired molded product by a molding method such as injection molding, extrusion molding or compression molding.

[0070]

The thermoplastic copolymer of the present invention has the same transparency and mechanical strength as AS resin, and has heat resistance comparable to that of polycarbonate. For example, it is preferably used as a molding material for automobile parts, industrial parts, home electric appliance parts and the like. Further, the copolymer of the present invention has good miscibility with AS resin and ABS resin, and these resins can be mixed and resin-blended for the purpose of improving the heat resistance thereof. Furthermore, since the amount of unreacted N-substituted maleimide remaining in the copolymer is extremely small, it does not pose a safety and health problem. The resin composition of the present invention using the thermoplastic copolymer is excellent in chemical resistance, impact resistance, heat resistance, and gives a molded article having good mechanical strength, and also has good moldability. It is suitable for use as a material for automobile interior parts such as console boxes, speaker boxes, instrument panels, air spoilers, radiator covers, or housings such as word processors and personal computers, and electrical and electronic products such as chassis. To be

[0071]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. In addition, each physical property was calculated | required by the following method.

(1) Copolymer composition It was determined by nitrogen analysis and H-NMR measurement. (2) Amount of remaining N-phenylmaleimide Copolymer 1.25 g was weighed into a 25 ml volumetric flask to prepare 25 ml of methyl ethyl ketone solution, and GC
Analysis was performed to determine the amount of residual N-phenylmaleimide. (3) Acetone insoluble matter 3 g of the copolymer was dissolved in 27 g of acetone, and the insoluble matter was visually confirmed.

(4) Molecular weight (Mw, Mn) Gel permeation chromatography analysis was carried out by the same method as for normal homopolystyrene, and Mw, Mn was determined using a calibration curve prepared using standard polystyrene.
I asked.

(5) Composition distribution of copolymer (I) About 100 mg of the copolymer was precisely weighed, put into a 10 ml volumetric flask, and dissolved in tetrahydrofuran (THF) to a constant volume. 100 μl of this is injected into a GPC apparatus and the molecular weight distribution is measured. On the other hand, in measuring the molecular weight distribution,
If a peak begins to appear on the chart, it is separated into sample bottles every 1 minute of outflow time, a certain amount of KBr powder is added to this, and then THF is evaporated and infrared absorption measurement is performed by the diffuse reflection method. To do. The composition ratio of each fraction is C
N group (2237 cm ⁻¹ ), C═O group (1712 cm
⁻¹ ) and the absorption intensity of the benzene ring (760 cm ⁻¹ ) are prepared in advance and can be determined by measuring using a calibration curve.

(6) Rubber Particle Size A calibration curve was prepared which shows the relationship between the latex particle size determined by electron microscopy and the absorbance at a wavelength of 550 nm of a diluted solution of the latex (50 ppm solids). It read from the calibration curve by measuring.

(7) Gel% of Multilayer Graft Copolymer Particles (V) The sample was dipped in 25 times the amount of acetone, shaken for 2 hours, and then the supernatant was removed with a centrifuge. This operation was repeated 3 times. After that, the weight ratio of the sample obtained by drying and the initial sample was expressed as a percentage and calculated.

(8) Physical Properties Each physical property was determined according to the following measuring methods. Haze: ASTM D1746 Heat distortion temperature: ASTM D648 (1/4, 18.6)
kg / cm ² under load) Tensile strength: ASTM D638 Bending strength: ASTM D790 Bending elastic modulus: ASTM D790 Tensile elongation: ASTM D638 Izod impact strength: ASTM D256 MI: JIS K7210 (250 ° C, 10 kg load) Gloss : ASTM D253

(9) Molding processability In the case where oligomers, residual phenylmaleimide, etc. adhere to the mold during injection molding, molding becomes difficult XX, molding is rather difficult, Δ, continuous molding without any problems. It is possible to do it.

Example 1 36 parts by weight of styrene, 14 parts by weight of acrylonitrile, N
-Phenylmaleimide 20 parts by weight, ethylbenzene 30
Parts by weight and 0.02 parts by weight of t-butylperoxyisopropyl carbonate at a rate of 1.26 liters / hr with a complete mixing reactor with a reaction volume of 1.9 liters and a laminar flow reaction of 0.5 liters. The reactors (three units) were continuously supplied to a polymerization tank arranged in series, and polymerization was carried out under the conditions of a complete mixing reactor temperature of 109 ° C and a laminar flow reactor temperature of 110 to 140 ° C. In addition, 10 parts by weight of styrene was added and mixed upstream of the second laminar flow reactor. The concentration of residual N-phenylmaleimide in the reaction liquid at the outlet of each reactor was 6.0% by weight, 0.35% by weight, 0.025% by weight and 0.0018% by weight in order from the first reactor. .

Then, a polymer solution having a solid content of 50% by weight was added to 2 parts.
At the same time it is heated to 65 ° C, it is introduced into a 20 Torr vacuum chamber,
The devolatilization was carried out for 15 minutes, the molten polymer was taken out, cooled and solidified to obtain a copolymer (I). This copolymer (I) is N
-Residual amount of phenylmaleimide is 18 ppm, styrene (ST) unit is 50% by weight, acrylonitrile (AN)
Unit: 17% by weight and N-phenylmaleimide (NPM
I) consisted of 33% by weight of units. The weight average molecular weight Mw (in terms of polystyrene) was 185,000, and the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn was 1.96.

When this copolymer was molded at 260 ° C. and the haze was determined, it was 2.1%. Further, this copolymer has no acetone insoluble content and has a heat distortion temperature of 138 ° C.
Tensile strength 670 kg / cm ² , bending strength 920 kg /
cm ² , a flexural modulus of 39,800 kg / cm ² ,
Further, regarding molding processability, continuous molding was possible without any problems. The charged composition is shown in Table 1, the composition distribution of the copolymer (composition for each molecular weight category) is shown in Table 2, and the composition and physical properties of the copolymer are shown in Table 3.

Examples 2 to 4 and Comparative Examples 1 and 2 A copolymer (I) was produced in the same manner as in Example 1 except that the charging composition was changed as shown in Table 1. Table 2 shows the composition distribution of the copolymers of Examples 2 to 4, and Table 3 shows the compositions and physical properties of the copolymers of Examples 2 to 4 and Comparative Examples 1 and 2.

[0083]

[Table 1] Note) ST: Styrene AN: Acrylonitrile NPMI: N-Phenylmaleimide EB: Ethylbenzene BPPC: t-Butylperoxyisopropyl carbonate

[0084]

[Table 2]

[0085]

[Table 3]

[0086]

[Table 4]

Comparative Example 3 0.05 part by weight of sodium dioctylsulfosuccinate,
A 60-liter reactor was charged with 30 liters of an aqueous solution containing 0.02 parts by weight of ammonium persulfate and 200 parts by weight of water, and the internal temperature was controlled at 60 ° C. Then 100 parts by weight of a monomer mixture consisting of 15% by weight of acrylonitrile, 54.8% by weight of styrene, 30% by weight of phenylmaleimide and 0.20% by weight of t-dodecyl mercaptan are added to this reactor, after the addition at 55 ° C. The polymerization was continued for 2 hours at 70 ° C. and then continued at 70 ° C. for 6 hours. The reaction rate was 96%. The composition distribution of this copolymer is shown in Table 4.

When this copolymer was molded at 260 ° C. and the haze was determined, it was 4.5%. Table 3 shows the composition and physical properties of this copolymer.

Comparative Example 4 36 parts by weight of styrene, 14 parts by weight of acrylonitrile, N
-Phenylmaleimide 20 parts by weight, ethylbenzene 30
Polymerization was carried out by continuously supplying a mixed solution of 1 part by weight and 0.02 part by weight of t-butylperoxyisopropyl carbonate to a completely mixed reactor having a reaction volume of 1.9 l at a rate of 1.26 l / hr. . The temperature of the complete mixing tank was 109 ° C.

Then, a polymer solution having a solid content of 50% by weight was added to 2 parts.
At the same time it was heated to 65 ° C, it was introduced into a 10 Torr vacuum chamber,
Devolatilization was carried out for 30 minutes. However, the residual N-phenylmaleimide in the copolymer was 2325 ppm. When this copolymer was molded at 260 ° C. and the haze was determined, 3.
2%, and the yellowness showed a large value. The composition distribution of the copolymer was uniform as in Example 1. Table 3 shows the composition and physical properties of this copolymer.

Comparative Example 5 In Comparative Example 4, the charge composition was 50 parts by weight of styrene, 16 parts by weight of acrylonitrile, and 4 parts of N-phenylmaleimide.
Polymerization was carried out in the same manner as in Comparative Example 4 except that 0 parts by weight and 30 parts by weight of ethylbenzene were used. Table 3 shows the composition and physical properties of the obtained copolymer.

Example 5 (1) Production of Copolymer (II) Polymerization was carried out in the same manner as in Example 1 using a monomer mixture consisting of 30% by weight of acrylonitrile and 70% by weight of styrene to obtain a copolymer. (II) was produced. The Mw (in terms of polystyrene) of this copolymer (II) is 100,000, Mw /
Mn was 1.9. (2) Preparation and Evaluation of Composition 50 parts by weight of the copolymer (I) obtained in Example 1 and 50 parts by weight of the copolymer (II) obtained in (1) above were mixed with P
Pellets were obtained by melt blending with a CM 45 mmφ extruder. Next, injection molding this pellet to create a test piece,
Physical properties were evaluated. The result, together with the composition of the copolymer,
It is shown in Table 5.

Examples 6 to 8 (1) Production of copolymer (II) In the same manner as in Example 5 (1), a copolymer (II) having the composition shown in Table 5 was obtained. (2) Preparation and Evaluation of Composition As the copolymer (I), those obtained in Examples 2 to 4 were used, and the copolymer (I) obtained in the above (1) was used.
I) was melt-blended in the proportions shown in Table 5 in the same manner as in Example 5 to obtain pellets, and then test pieces were prepared to evaluate physical properties. The results are shown in Table 5.

[0094]

[Table 5]

Example 9 (1) Production of Copolymer (II) Polymerization was carried out in the same manner as in Example 1 using a monomer mixture consisting of 30% by weight of acrylonitrile and 70% by weight of styrene to obtain a copolymer. (II) was produced. The Mw (in terms of polystyrene) of this copolymer (II) is 100,000, Mw /
Mn was 1.9. (2) Production of Copolymer (IV) 40 parts by weight of butadiene rubber (polybutadiene latex manufactured by Nippon Zeon Co., Ltd., particle size: 3000 A), 0.05 part by weight of sodium dihexyl sulfosuccinate, 0.02 part by weight of ammonium persulfate, 200 parts by weight of water. Aqueous solution consisting of 30
Charge 60 liter reactor to the internal temperature of 75 ℃
Was controlled. Next, 35% by weight of acrylonitrile, 55% by weight of styrene, 1-N-phenylmaleimide
40 parts by weight of a monomer mixture consisting of 0% by weight are continuously added to this reactor at 55 ° C. for 2 hours, and after addition is complete, a further 6
The polymerization was continued for hours. The reaction rate was 96%. The composition of the copolymer (IV) thus obtained was 40% by weight of a rubber component, 33% by weight of a styrene unit, 21% by weight of an acrylonitrile unit and 6% by weight of an N-phenylmaleimide unit.

(3) Preparation and Evaluation of Composition 55 parts by weight of the copolymer (I) obtained in Example 1, 10 parts by weight of the copolymer (II) obtained in the above (1) and the above (2) 35 parts by weight of the copolymer (IV) obtained in 1) above, and 0.3 parts by weight of a mixture of titanium oxide, a perinone anthraquinone red dye and a heterocyclic yellow dye as a dye and pigment. MIX 45 made by Ikegai Tekko Co., Ltd.
Melt kneading was performed at 260 ° C. with an mmφ extruder to obtain pellets. Then, the pellets were molded by an injection molding machine to obtain test pieces for measuring physical properties. No thermal discoloration was observed even when this test piece was heated at 110 ° C. for 2 hours, and when immersed in gasoline at 20 ° C. for 48 hours, the gasoline resistance was good and no change in appearance was observed. . Furthermore, when it is coated with acrylic paint, it has good appearance smoothness,
The sharpness was good. Table 6 shows the physical properties of the test piece together with the component composition of the composition.

Examples 10 to 13 The copolymer (I), the copolymer (II) and the copolymer (III) having the compositions shown in Table 6 were prepared in Example 1 and Example 5, respectively.
Test pieces were prepared in the same manner as in Example 9 except that the components were produced in the same manner as in (1) and Example 9 (2), and were mixed in the proportions shown in Table 6. The heat discoloration resistance, gasoline resistance, coating appearance smoothness, and sharpness of these test pieces were the same as in Example 9. Table 6 shows the physical properties.

[0098]

[Table 6] Note 1) Test piece with a sunshine weatherometer at 63 ° C
2000 hours exposure test was conducted, and the appearance was visually observed.

Example 14 (1) Production of Copolymer (III) As the first stage polymerization, 80% by weight of methyl methacrylate was used.
63 parts by weight of a monomer mixture consisting of 99% by weight of butyl acrylate and 1.0% by weight of triallyl isocyanurate as a second stage polymerization. As a third polymerization, 27 parts by weight of a monomer mixture consisting of 40% by weight of acrylonitrile and 60% by weight of styrene was used for ordinary emulsion polymerization at 75 ° C., and the copolymer (II
I) was obtained.

(2) Preparation and evaluation of composition In Example 10, pellets were obtained in the same manner as in Example 10 except that the copolymer (III) obtained in the above (1) was used. After that, a test piece was prepared. MF
I was 6.0 g / 10 minutes, HDT was 113 ° C., and Izod impact strength was 14 kg · cm / cm. In addition, this test piece was measured with a sunshine weatherometer at 20 ° C at 63 ° C.
When a 00-hour weather resistance test was performed, there was almost no change in appearance.

Example 15 A glass fiber roving consisting of 500 to 20,000 fibers was aerated with 25% by weight of acrylonitrile units and 7 styrene units.
It was dipped in an aqueous emulsion of a copolymer containing 5% by weight, dried, and bundled. Then, using an extruder, the strand obtained by extrusion coating 20 parts by weight of the glass fiber having the above-mentioned focusing treatment with 80 parts by weight of the copolymer (I) obtained in Example 1 was cut. , GF reinforced pellets were prepared. The pellets were molded by an injection molding machine, test pieces for measuring physical properties were prepared, and physical properties were evaluated. Table 7 shows the results.

Example 16 Same as Example 15 except that copolymer (I), (II), (III) shown in Table 7 was used in place of copolymer (I) in Example 15. After obtaining the pellets, a test piece was prepared and the physical properties were evaluated. Table 7 shows the results.

[0103]

[Table 7] Note 1) MFR: 250 ° C, load: 10 kg. 2) The injection molded pieces were evaluated by visual observation.

Example 17 10 parts by weight of the copolymer (I) obtained in Example 1, 20 parts by weight of the copolymer (II) obtained in Example 5 and the copolymer obtained in Example 9 (IV) 20 parts by weight of polycarbonate "NOVAREX 7035A" [manufactured by Mitsubishi Kasei Co., Ltd., trade name] were blended using a PCM 45 mmφ extruder and extrusion kneaded to prepare pellets. Next, the pellets were molded by an injection molding machine, test pieces for measuring physical properties were prepared, and physical properties were evaluated. As a result, MFR
(250 ° C., 10 kg) was 8.4 g / 10 minutes, Izod impact strength was 11.7 kg · cm / cm, heat distortion temperature was 124 ° C., and flexural modulus was 26,000 kg / cm ² .

Example 18 (1) Production of Multilayer Graft Copolymer Particles (V) (b) Preparation of Hard Resin Layer (First Layer) as Inner Layer-Seed First Stage Polymerization Ion-exchanged water 248 in reactor Then, 0.3 part by weight and 0.05 part by weight of sodium dihexylsulfosuccinate were charged, and nitrogen substitution was sufficiently performed while stirring, and then the temperature was raised to an internal temperature of 75 ° C. After adding 0.02 parts by weight of ammonium persulfate to this reactor, 8 parts by weight of methyl methacrylate,
A mixture of 2 parts by weight of butyl acrylate was added continuously over 50 minutes. After addition, ammonium persulfate 0.0
After adding 1 part by weight, the reaction was continued at 75 ° C. for 45 minutes. The polymerization rate was 99%, and the particle size of latex was 0.
It was 17 μm.

Second-stage polymerization of seed Next, 1/4 of this latex (2.5 parts by weight in terms of solid content) was taken out, and 186.2 parts by weight of ion-exchanged water and sodium dihexylsulfosuccinate 0.03 Part by weight was charged into a reactor, and nitrogen substitution was sufficiently performed while stirring, and then the temperature was raised to an internal temperature of 75 ° C. After 0.02 part by weight of ammonium persulfate was added to this reactor, a mixture of 6.0 parts by weight of methyl methacrylate and 1.5 parts by weight of butyl acrylate was continuously added over 50 minutes. After the addition was completed, the reaction was continued at 75 ° C. for 45 minutes in order to complete the reaction. The polymerization rate was 98%, and the particle size of the latex was 0.28 μm.

(B) Preparation of acrylic acid ester-based crosslinked polymer layer (second layer) In the presence of the latex containing the hard resin particles obtained in (a) above, 0.01 part by weight of ammonium persulfate and dihexyl were added. After adding 0.05 part by weight of sodium sulfosuccinate, a mixture of 63 parts by weight of butyl acrylate and 1.2 parts by weight of triallyl isocyanurate as a crosslinking agent was continuously added at 70 ° C. over 80 minutes. After the addition was completed, the reaction was continued at 70 ° C. for 20 minutes. The polymerization rate through one layer and two layers is 85%, and the particle size is 0.41μ.
m.

(C) Preparation of rubber-like elastic material layer (third layer) After completion of the step (b), unreacted butyl acrylate 11
In the presence of 0.18 parts by weight of triallyl isocyanurate, 0.045 parts by weight of ammonium persulfate and 0.45 parts by weight of sodium dihexylsulfosuccinate are added, followed by 3.8 parts by weight of acrylonitrile and 11.4 parts of styrene.
A mixture of parts by weight and 0.025 parts by weight of t-dodecyl mercaptan was added continuously at 75 ° C. over 90 minutes. The polymerization rate was 93%. Further, the amount of residual monomers in the latex was measured by gas chromatography and the copolymerization composition ratio of the three layers was calculated. As a result, the weight ratio of acrylonitrile unit / styrene unit / butyl acrylate unit was 10/43/47. It was

(D) Preparation of resin layer (fourth layer) In the presence of the latex of (c), acrylonitrile 2.
A mixture of 95 parts by weight, 8.86 parts by weight of styrene and 0.02 parts by weight of t-dodecyl mercaptan was added continuously at 75 ° C. over 70 minutes. Further, the reaction was continued at 85 ° C. for 1 hour to complete the polymerization. The polymerization rate is 97
%, And the particle size was 0.56 μm. Further, the amount of residual monomer in the latex was measured by gas chromatography to calculate the copolymerization composition ratio of the four layers. As a result, the weight ratio of acrylonitrile unit / styrene unit / butyl acrylate unit was 24/65/11. there were. The latex thus obtained was salted out with aluminum sulfate according to a conventional method and dried to obtain multilayer graft copolymer particles (V).

(2) Preparation and Evaluation of Composition The copolymer (I) obtained in Example 1 and the multilayer graft copolymer particles (V) obtained in the above (1) are mixed in the multilayer graft. After mechanical mixing such that the amount of butyl acrylate units in the copolymer particles (V) was 22% by weight based on the weight of the composition (multilayer graft copolymer particles (V) /
Copolymer (I) weight ratio 35/65) was kneaded in a melt extruder at 250 ° C. and pelletized. Next, using the pellets, various test pieces were prepared by an injection molding machine, and various physical properties were evaluated. The results are shown in Table 9. Table 8 shows the composition, gel% and particle size of the multilayer graft copolymer (V). From Tables 8 and 9, it can be seen that the resin composition of the present invention has high impact strength and excellent appearance.

Example 19 The copolymer (I) obtained in Example 1, the multilayer graft copolymer (V) obtained in Example 18 and the copolymer (II) obtained in Example 5 were prepared. The mixture was mechanically mixed at a weight ratio of 55/35/10, and then kneaded with a melt extruder at 250 ° C. to form pellets. Using the pellets, various test pieces were prepared by an injection molding machine and the physical properties were evaluated. The results are shown in Table 9.

Comparative Example 6 (1) Production of Multilayer Graft Copolymer Particles (V) (a) Preparation of Innermost Hard Resin Layer (First Layer) The same procedure as in Example 18 (a) was carried out. (B) Acrylic acid ester-based crosslinked polymer layer (second layer)
In the presence of the latex obtained in (a) above, 0.13 parts by weight of ammonium persulfate and 0.05 parts by weight of sodium dihexylsulfosuccinate were added, and then butyl acrylate 6 was added.
A mixture of 3 parts by weight and 1.2 parts by weight of triallyl isocyanurate as a crosslinking agent was continuously added at 80 ° C. over 80 minutes. After the addition was completed, the reaction was continued at 80 ° C. for 90 minutes. Polymerization rate through 1 layer and 2 layers is 99.5%
And the particle size was 0.41 μm.

(C) Preparation of Resin Layer In the presence of the latex obtained in (b) above, 0.045 parts by weight of ammonium persulfate and 0.45 parts by weight of sodium dihexylsulfosuccinate were added, and then 6.75 parts by weight of acrylonitrile. Parts, styrene 20.25 parts by weight and t-
A mixture consisting of 0.045 parts by weight of dodecyl mercaptan was added continuously at 75 ° C. over 160 minutes. Further, the reaction was continued at 85 ° C. for 1 hour to complete the polymerization.
The polymerization rate was 98%, and the particle size was 0.55 μm. The amount of residual monomers in the latex was measured by gas chromatography to calculate the copolymerization composition ratio of the resin layer. As a result, the weight ratio of acrylonitrile unit / styrene unit / butyl acrylate unit was 25/75/0.
The latex thus obtained was treated in the same manner as in Example 18 and evaluated. Table 8 shows the results.

[0114]

[Table 8] Note) MMA: Methyl methacrylate BA: Butyl acrylate AN: Acrylonitrile ST: Styrene

(2) Preparation and Evaluation of Composition Multilayer graft copolymer particles (V) obtained in the above (1)
After the pellets were obtained in the same manner as in Example 18 except that the above was used, test pieces were prepared and the physical properties were evaluated. The results are shown in Table 9.

[0116]

[Table 9]

From Tables 8 and 9, it can be seen that the multilayer graft copolymer particles having no rubbery elastic layer have a low gel% and a low Izod impact strength.

Comparative Example 7 In Example 18, the multilayer graft copolymer particles (V) were used.
It was carried out in the same manner as in Example 18 except that triallyl isocyanurate was not used as a cross-linking agent in the production of the (2) acrylic acid ester-based cross-linked polymer layer (second layer) in the production. The results are shown in Table 10. From Table 10, it can be seen that when the triallyl isocyanurate was not used, the resulting composition was significantly inferior to Example 18 in mechanical properties such as impact strength.

Comparative Example 8 In Example 18, the multilayer graft copolymer particles (V) were used.
Except that 1.2 parts by weight of allyl methacrylate as a grafting agent was used in place of triallyl isocyanurate as a cross-linking agent in the preparation of the (2) acrylic acid ester-based cross-linked polymer layer (second layer) in the production of Example 18
It carried out similarly to. The results are shown in Table 10. Table 1
From 0, in the case of using allyl methacrylate as a grafting agent instead of triallyl isocyanurate as a crosslinking agent,
It can be seen that the resulting composition has a lower impact strength as compared to Example 18.

[0120]

[Table 10]

Examples 20 to 22, Comparative Examples 9 and 10 In Example 18, seed polymerization was carried out by reducing the amount of the latex obtained by the first-stage polymerization of the hard resin (1 layer) of the innermost layer. By continuing, the final particle size was suppressed to 0.56 to 0.85 μm. In addition, the final particle size was reduced to 0. by increasing the amount of sodium dihexyl sulfosuccinate in the first stage of the seed and continuing the seed polymerization.
It was suppressed to 56 to 0.16 μm. The latex thus obtained was treated in the same manner as in Example 18 to obtain multilayer graft copolymer particles (V), and then a composition was prepared and evaluated in the same manner as in Example 18. Table 11 shows the results. According to Table 11, when the particle size of the multilayer graft copolymer is smaller than 0.2 μm, the resulting composition has excellent gloss, but the impact strength is low, while when it exceeds 0.80 μm, the impact strength is excellent. However, the gloss is low.

[0122]

[Table 11]

Comparative Examples 11 and 12 In Example 18, instead of the copolymer (I) which is the matrix resin, an acrylonitrile-styrene copolymer (manufactured by Asahi Kasei Kogyo Co., Ltd., trade name; Stylak AS-7) was used.
No. 83) (Comparative Example 12), an ABS resin (Asahi Kasei Kogyo KK, trade name Stylak ABS) (Comparative Example 13) and the compositions of Examples 18 and 19, The heat distortion temperature was measured by a method according to ASTM D648. In addition, a weather resistance accelerating test using a due panel light control weather meter was also performed. Table 12 shows the results. Table 12 shows that the resin composition of the present invention is superior in heat resistance and weather resistance to the resin compositions of Comparative Examples.

[0124]

[Table 12] Note 1) Suga Test Instruments Co., Ltd. Dew panel optical control weather meter (DPWL-5 type)
A weather resistance accelerated test was conducted in a cycle of irradiation at 0 ° C and wet dew condensation at 40 ° C.

Example 23 80 parts by weight of the composition of Example 18 and 20 parts by weight of glass fiber which had been bundle-treated in the same manner as in Example 15 were extrusion-coated with an extruder to cut a strand. Then, a GF-reinforced pellet was prepared. Next, this pellet is molded with an injection molding machine to create a test piece for measuring physical properties,
Physical properties were evaluated. As a result, the tensile strength is 1110 kg /
cm ² , elongation 4%, bending strength 1480 kg / cm ² , Izod impact strength 13.6 kg · cm / cm, and heat distortion temperature 137 ° C.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C08L 33/18 C08L 33/18 51/04 51/04 69/00 69/00 // (C08F 212/08 220 : 42 222: 40) (C08F 220/42 212: 08 222: 40) (C08F 222/40 212: 08 220: 42)

Claims (15)

[Claims] 1. (a) Aromatic vinyl compound units 30 to 7
A copolymer consisting of 0 to 40% by weight of (b) vinyl cyanide compound unit (4 to 40% by weight) and (c) 26 to 50% by weight of N-substituted maleimide unit, which has a copolymerization weight of each molecular weight group measured by GPC. The distribution of the coalescence composition is narrow, the acetone insoluble matter is not substantially contained, and the weight average molecular weight is 100,000 to 30.
A thermoplastic copolymer having a number average molecular weight of 50,000 to 150,000 and a residual amount of unreacted N-substituted maleimide of 50 ppm or less. 2. The weight ratio of (A) polycarbonate resin to (A) the thermoplastic copolymer according to claim 1 is 1/9.
A thermoplastic resin composition blended in a range of 9/1. 3. A thermoplastic resin according to claim 1, wherein (G) at least one inorganic filler selected from glass fibers and glass flakes is added in a weight ratio of 1 /.
A thermoplastic resin composition prepared by blending in the range of 9 to 4/6. 4. (A) 30 to 70% by weight of the thermoplastic copolymer according to claim 1, (B) 50 to 80% by weight of (d) aromatic vinyl compound unit and (v) vinyl cyanide compound unit. 50 to 20% by weight of weight average molecular weight 80,000 to 3
A thermoplastic resin composition containing 70,000 to 30% by weight of a thermoplastic copolymer of 0,000. 5. A thermoplastic resin composition comprising the composition according to claim 4 and (F) a polycarbonate resin in a weight ratio of 1/9 to 9/1. 6. The composition according to claim 4, wherein (G) at least one inorganic filler dispersed in glass fibers and glass flakes is blended in a weight ratio of 1/9 to 4/6. A thermoplastic resin composition comprising: 7. (A) 30 to 70% by weight of the thermoplastic copolymer according to claim 1, (B) 50 to 80% by weight of (d) aromatic vinyl compound unit and (v) vinyl cyanide compound unit. 50 to 20% by weight of weight average molecular weight 80,000 to 3
5 to 30% by weight of a thermoplastic copolymer of 0,000 and (C) Tg
Having a monomer mixture of an aromatic vinyl compound and a vinyl cyanide compound in at least one rubber component selected from acrylate rubbers and diene rubbers having a temperature of 25 ° C. or less in the resulting copolymer. The ratio of each unit is in the range of 50:50 to 80:20 by weight, and the thermoplastic graft copolymer 25 obtained by graft polymerization so that the content of the rubber component is 30 to 60% by weight. Four
A thermoplastic resin composition containing 5% by weight. 8. A thermoplastic resin composition comprising the composition according to claim 7 and (F) a polycarbonate resin in a weight ratio of 1/9 to 9/1. 9. The composition according to claim 7, wherein (G) at least one inorganic filler selected from glass fibers and glass flakes is used in a weight ratio of 1/9 to 4/6. A thermoplastic resin composition formed by blending. 10. (A) 30 to 70% by weight of the thermoplastic copolymer according to claim 1, (B) 50 to 80% by weight of (d) aromatic vinyl compound unit and (v) vinyl cyanide compound unit. Weight average molecular weight of 50 to 20% by weight 80,000 to
5 to 30% by weight of 300,000 thermoplastic copolymer, and (D) T
A monomer mixture of an aromatic vinyl compound, a vinyl cyanide compound, and N-phenylmaleimide was obtained in at least one rubber component selected from acrylate rubbers and diene rubbers having a g of 25 ° C. or less. The ratio of the aromatic vinyl compound unit to the vinyl cyanide compound unit in the copolymer is in the range of 50:50 to 80:20 by weight, and the content of the N-phenylmaleimide unit is 5 to 1
A thermoplastic resin composition comprising 0 to 25% by weight of a thermoplastic graft copolymer obtained by graft polymerization at a rubber component content of 30 to 60% by weight. 11. A composition according to claim 10, wherein
(F) Polycarbonate resin, weight ratio 1/9 to 9/1
A thermoplastic resin composition prepared by blending within the range. 12. The composition according to claim 10,
(G) At least one inorganic filler selected from glass fibers and glass flakes, in a weight ratio of 1/9 to 4 /
A thermoplastic resin composition prepared by blending in the range of 6. 13. (A) 30 to 70% by weight of the thermoplastic copolymer according to claim 1, and (E) (a) a hard resin particle having an acrylic ester cross-linked polymer layer on the surface thereof. 30 to 80% by weight of rubber-like copolymer particles provided such that the weight ratio of the polymer to the polymer layer is 5:95 to 40:60.
And (b) acrylic acid ester units 20 to 20 provided on the surface of the rubbery copolymer particles by graft polymerization in sequence.
10 to 30% by weight of a rubber-like elastic body layer comprising 80% by weight, 5 to 75% by weight of an aromatic vinyl compound unit, and 5 to 50% by weight of a vinyl cyanide compound unit, and (c) an aromatic vinyl compound unit of 30 to 90% Resin layers 10 to 4 comprising 10% by weight of vinyl cyanide compound units and 20% by weight or less of acrylic acid ester units optionally introduced.
An average particle size of 0.2 to 0.8 μ composed of 0% by weight
from 25 to 45% by weight of the multi-layered graft copolymer particles of m, and optionally 50 to 80% by weight of (B) (d) aromatic vinyl compound unit and (e) vinyl cyanide compound unit of 20 to 20% by weight. Consisting of weight average molecular weight of 80,000-30
A thermoplastic resin composition containing 50% by weight or less of a thermoplastic copolymer. 14. A composition according to claim 13, wherein
(F) Polycarbonate resin, weight ratio 1/9 to 9/1
A thermoplastic resin composition prepared by blending within the range. 15. The composition according to claim 13, wherein
(G) At least one inorganic filler selected from glass fibers and glass flakes, in a weight ratio of 1/9 to 4 /
A thermoplastic resin composition prepared by blending in the range of 6.