JP2003292715A - Thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition as a resin material simultaneously meeting impact resistance, thermal decomposition resistance, appearance after molded such as non-discoloration and gloss, and high-level weatherability. <P>SOLUTION: This thermoplastic resin composition comprises (A) a maleimide- based copolymer having such monomer units composition that in triangular coordinates made up from an N-substituted maleimide, an alkyl(meth)acrylate unit and another copolymerizable monomer, the corresponding proportion of the monomer units fall within a region formed by joining a-point, b-point, c-point and d-point together and (B) a graft copolymer obtained by graft polymerization of at least one kind of vinyl monomer to a polyorganosiloxane/alkyl(meth) acrylate composite rubber. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to heat resistance, weather resistance,
Maleimide resin composition excellent in impact resistance and thermal decomposition resistance, more specifically, maleimide resin composition composed of maleimide copolymer and polyorganosiloxane / alkyl (meth) acrylate composite rubber graft copolymer It is about.

[0002]

2. Description of the Related Art In recent years, demands for heat resistance and impact resistance of resin materials have become higher. Especially automotive parts such as meter hoods, instrument panels,
Interior parts such as console boxes are required to have good heat resistance and impact resistance as well as good injection moldability as the parts become larger. The injection molding is preferably capable of molding in a wide temperature range, and is particularly required to be capable of molding without causing thermal decomposition at high temperatures. Further, in exterior parts such as an outer plate and a lamp housing, it is required that the thermoplastic resin is excellent in weather resistance in addition to heat resistance and impact resistance.

As a resin material having high heat resistance and impact resistance used in such a field, a maleimide copolymer obtained by copolymerizing an aromatic vinyl compound and a vinyl cyanide compound with an N-substituted maleimide compound is used as a matrix. The following thermoplastic resins are known. Japanese Patent Laid-Open No. 4-63854
The publication describes a method of adding a graft copolymer obtained by graft-polymerizing a vinyl-based monomer to a polyorganosiloxane / alkyl (meth) acrylate composite rubber to a maleimide-based copolymer. Also, JP-A-64-08
7651 and JP-A-8-053591 describe a method of adding a graft copolymer obtained by graft-polymerizing a vinyl-based monomer to a polybutadiene / butyl acrylate composite rubber to a maleimide-based copolymer. .

Further, JP-A-2000-143929 proposes a transparent thermoplastic resin composition in which a specific maleimide copolymer and a rubber-modified thermoplastic resin having a refractive index close to that of the specific maleimide copolymer are added. However, the conventional thermoplastic resin composition comprising a maleimide-based copolymer modified with a rubber-like polymer cannot be said to have a high level of weather resistance required in recent years, and the coloring property and the The molding appearance such as gloss characteristics was also unsatisfactory in the field of products used without coating. Further, during the molding process in the high temperature range, a defective appearance was observed due to the occurrence of silver streaks due to the thermal decomposition of the resin.

[0005]

The object of the present invention is to provide a maleimide resin composition modified with a rubbery polymer with a molded appearance such as impact resistance, thermal decomposition resistance, colorability and gloss, and a high level. It is to develop a resin material that simultaneously satisfies weather resistance.

[0006]

Means for Solving the Problems As a result of intensive studies made by the present inventors in view of the above-mentioned situation, a thermoplastic resin excellent in heat resistance, thermal decomposition resistance, impact resistance, weather resistance and molding appearance is obtained. To obtain the composition, a graft copolymer (hereinafter referred to as a graft copolymer) obtained by graft-polymerizing a vinyl-based monomer onto a composite rubber composed of a polyorganosiloxane and a polyalkyl (meth) acrylate rubber is specified. By blending with a maleimide-based copolymer of composition, it has excellent heat resistance and impact resistance, and further has thermal decomposition resistance, molding appearance,
The present invention has been accomplished by finding that the thermoplastic resin composition has excellent weather resistance.

That is, according to the present invention, the N-
In triangular coordinates composed of a substituted maleimide, an alkyl (meth) acrylate unit and another copolymerizable monomer, point a (N-substituted maleimide 1% by mass, alkyl (meth) acrylate unit 1% by mass, copolymerization Other possible monomers 98% by mass), point b (N-substituted maleimide 1% by mass,
Alkyl (meth) acrylate unit 30% by mass, other copolymerizable monomer 69% by mass), point c (N-substituted maleimide 71% by mass, alkyl (meth) acrylate unit 2
9% by weight, 0% by weight of other copolymerizable monomer), and d
Dots (99% by mass of N-substituted maleimide, alkyl (meth))
Acrylate unit 1% by mass, other copolymerizable monomer 0
1% or 2 in the maleimide-based copolymer (A) having a monomer unit composition and the polyorganosiloxane / alkyl (meth) acrylate composite rubber (S) in the region formed by connecting the four points. The present invention provides a thermoplastic resin composition containing a graft copolymer (B) obtained by graft-polymerizing one or more vinyl monomers. Hereinafter, the present invention will be described in detail.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The maleimide-based copolymer (A) used in the present invention comprises an N-substituted maleimide and an alkyl (meth) acrylate unit as essential components, and is optionally copolymerizable. It is a copolymer of the monomer. The N-substituted maleimide is not particularly limited, but examples thereof include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, N-. i
-Butylmaleimide, Nt-butylmaleimide, N-
Examples thereof include N-cycloalkylmaleimides such as cyclohexylmaleimide, N-phenylmaleimides represented by the following general formula (1), N-arylmaleimides such as N-substituted phenylmaleimides, and N-aralkylmaleimides. One kind or two or more kinds can be used in combination.

[0009]

[Chemical 1] (In the formula, R ¹ , R ² , and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen.)

As the alkyl (meth) acrylate,
Although not particularly limited, for example, methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, -i-propyl methacrylate, -n-butyl methacrylate,
Methacrylate-i-butyl, methacrylate-t-butyl, amyl methacrylate, isoamyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, pendyl methacrylate, methacryl Phenyl acid, methyl acrylate, ethyl acrylate, -n-propyl acrylate, -i-propyl acrylate, -n-butyl acrylate, -i-butyl acrylate, -t-butyl acrylate, amyl acrylate, Isoamyl acrylate, octyl acrylate, acrylic acid-
2-ethylhexyl, decyl acrylate, lauryl acrylate, cyclohexyl acrylate, penzyl acrylate, phenyl acrylate and the like can be exemplified. Preferably, since it has excellent heat resistance and impact resistance, methyl methacrylate, ethyl methacrylate, methyl acrylate,
It is ethyl acrylate. These alkyl (meth) acrylate compounds may be used either individually or in combination of two or more.

Other copolymerizable monomers that can be used in the maleimide copolymer (A) include, for example, aromatic vinyl compounds and vinyl cyanide compounds, but preferably aromatic vinyl compounds. It is a compound. The aromatic vinyl compound is not particularly limited, but examples thereof include monovinyl aromatic hydrocarbon and monovinylidene aromatic hydrocarbon. Further, as the monovinyl aromatic hydrocarbon, styrene, o-, m- or p-
Mention may be made of methylstyrene (0-, m- or p-vinyltoluene), p-t-butylstyrene, o-, m- or p-chlorostyrene, 2,4-dipromostyrene, and also monovinylidene aroma. Α as a group hydrocarbon
-Methylstyrene, α-ethylstyrene and the like can be mentioned. Among these monovinyl aromatic hydrocarbons and monovinylden aromatic hydrocarbons, styrene, vinyltoluene and α-methylstyrene are preferable, and styrene and α-methylstyrene are more preferable. These aromatic vinyl compounds can be used alone or in combination of two or more. On the other hand, examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, ethacrylonitrile, maleonitrile, fumaronitrile, and the like, of which acrylonitrile is preferable. These vinyl cyanide compounds may be used either individually or in combination of two or more.

The composition of the maleimide-based copolymer (A) in the present invention is a in the compositional triangular coordinates shown in FIG.
Dots (1% by mass of N-substituted maleimide, 1% by mass of alkyl (meth) acrylate unit, other copolymerizable monomer 98)
Mass%), b point (1 mass% of N-substituted maleimide, 30 mass% of alkyl (meth) acrylate unit, 69 mass% of other copolymerizable monomer), c point (N-substituted maleimide 7).
1% by mass, alkyl (meth) acrylate unit 29% by mass, other copolymerizable monomer 0% by mass, and d point (N
It is used in a composition within a rectangular region formed by connecting 4 points of 99% by mass of substituted maleimide, 1% by mass of alkyl (meth) acrylate unit and 0% by mass of other copolymerizable monomer.

Preferably, (1% by mass of N-substituted maleimide, 1% by mass of alkyl (meth) acrylate unit and 98% by mass of other copolymerizable monomer), (1% by mass of N-substituted maleimide, alkyl ( (Meth) acrylate unit 30% by mass, other copolymerizable monomer 69% by mass), (N-substituted maleimide 70% by mass, alkyl (meth) acrylate unit 30% by mass, other copolymerizable monomer) 0% by mass), (N-substituted maleimide 70% by mass, alkyl (meth) acrylate unit 1% by mass, other copolymerizable monomer 29% by mass), and a rectangular region formed by connecting four points. And more preferably (N-substituted maleimide 1
Mass%, alkyl (meth) acrylate unit 1 mass%,
Other copolymerizable monomer 98% by mass), (N-substituted maleimide 1% by mass, alkyl (meth) acrylate unit 3)
0% by mass, 69% by mass of other copolymerizable monomer), (N
-Substituted maleimide unit 50% by mass, alkyl (meth) acrylate unit 30% by mass, other copolymerizable monomer 2
0% by mass) and (N-substituted maleimide unit 50% by mass, alkyl (meth) acrylate unit 1% by mass, other copolymerizable monomer 49% by mass) of a quadrangle formed. It is within the range of the area. The maleimide copolymer (A) having the above composition improves the property balance of the heat resistance, weather resistance, impact resistance, and thermal decomposition resistance of the thermoplastic resin.

The maleimide copolymer (A) can be produced by a known method such as emulsion polymerization, suspension polymerization and bulk polymerization. For example, as a production method by a suspension polymerization method, as a polymerization catalyst, an organic oxide such as benzoyl peroxide, t-butylperoxybenzoate, lauroyl peroxide, 1,1′-azobiscyclohexane-1-carbonitrile is used. , 1,1′-azobisisobutyronitrile and other azo compounds are used as the radical generator, and mercaptans such as t-dodecyl mercaptan and octyl mercaptan are used as molecular weight regulators. ), A copolymer of a sodium salt of methyl (meth) acrylate and 2-sulfoethyl methacrylate, a sparingly soluble phosphate such as hydroxyabatite, tricalcium phosphate, magnesium phosphate, barium sulfate, and calcium sulfate hydroxide. Inorganic compounds such as magnesium and magnesium carbonate, polyvinyl alcohol Lumpur, protective colloids such as methyl cellulose or the like may be carried out a polymerization reaction according to known methods using.

Further specific examples of the production of the maleimide type copolymer (A) will be given. For example, a polymerization catalyst and a molecular weight modifier are dissolved in one or two kinds of other monomers except N-substituted maleimide. , A method of carrying out polymerization by adding the solution to a reaction vessel containing water, a suspension stabilizer and the remaining monomer, and adding a polymerization catalyst, a molecular weight modifier and a suspension stabilizer to water in the reaction vessel. After that, a method in which a monomer is added simultaneously or in divided portions to carry out polymerization can be adopted. When the particle size of the maleimide copolymer (A) is produced by suspension polymerization, the dispersion conditions such as stirring conditions are adjusted so that the weight average particle size is 10 to 8000 μm, preferably 50 to 5000 μm. It is desirable to produce it from the viewpoint of kneading operability with the graft copolymer (B). Further, the molecular weight of the maleimide-based copolymer (A) has a mass average molecular weight of 10,000 to 300,000 because the resulting thermoplastic resin composition has an excellent balance of impact resistance and moldability.
It is preferably in the range of 0, more preferably 20,
It is in the range of 000 to 200,000.

As the graft copolymer (B), one kind or two or more kinds of compound rubber (S) (hereinafter simply referred to as compound rubber) composed of a polyorganosiloxane component and a polyalkyl (meth) acrylate rubber component is used. The vinyl-based monomer is graft-polymerized. Even if any one of polyorganosiloxane and polyalkyl (meth) acrylate rubber or a simple mixture thereof is used as a rubber source instead of the above composite rubber (S), a composition having excellent performance as shown in the present invention is obtained. Not obtained, the polyorganosiloxane component and the polyalkyl (meth) acrylate rubber component are combined to provide excellent impact resistance, mechanical strength,
A molded product having a molded appearance can be obtained.

The composition of the composite rubber (S) is not particularly limited, but the composition range may be such that the polyorganosiloxane component is 1 to 99% by mass and the polyalkyl (meth) acrylate rubber component is 99 to 1% by mass. It is preferable because the resin composition obtained has good impact resistance and good molding appearance.
More preferably, the polyorganosiloxane component is 5 to 8
0% by mass, and the polyalkyl (meth) acrylate rubber component is in the range of 95 to 20% by mass. Further, the average particle diameter of the composite rubber (S) is not particularly limited, but 0.01-1.
The thickness is preferably 0 μm, more preferably 0.03 to 0.15 μm.

The method for producing the composite rubber (S) is not particularly limited, but the emulsion polymerization method is preferred. First,
It is preferable that the polyorganosiloxane is prepared in advance by an emulsion polymerization method, and then the monomer for producing an alkyl (meth) acrylate rubber is emulsion-polymerized in the presence of the polyorganosiloxane. The polyorganosiloxane component constituting the composite rubber (S) can be adjusted by emulsion polymerization using the following organosiloxane and a crosslinking agent for polyorganosiloxane (hereinafter referred to as a crosslinking agent (I)). A siloxane graft crossing agent (hereinafter referred to as a graph and crossing agent (I)) can also be used in combination.

As the organosiloxane used here, various cyclic compounds having three or more membered rings can be used, and 3 to 6 can be used.
A membered ring is preferably used. Examples of 3- to 6-membered organosiloxanes include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentanesiloxane, dodecamethylcyclohexanetetrasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane. , Octaphenylcyclotetrasiloxane, and the like. These alone or 2
Used as a mixture of two or more species. The amount of organosiloxane used in the polyorganosiloxane component is 60% by mass or more, and preferably 70% by mass or more. As the cross-linking agent (I), a trifunctional (trialkoxysilane) or tetrafunctional (tetraalkoxysilane) silane compound is used, and trimethoxysilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra Examples thereof include n-propoxysilane and tetrabutoxysilane. Among these, tetrafunctional silane compounds are preferable, and tetraethoxysilane is particularly preferable.
The amount of the cross-linking agent (I) used is 0.1 to 30% by mass in the polyorganosiloxane component.

The graft crossing agent (I) has the following formula

[Chemical 2] (In each formula, R ⁴ represents a methyl group, R ⁵ represents a hydrogen atom or a methyl group, n represents 0, 1 or 2, and p is 1 to 6
The compound etc. which can form the unit represented by these are used.

Since the (meth) acryloyloxyalkylsiloxane capable of forming the unit represented by the formula (I-1) has a high grafting efficiency, it is possible to efficiently form a grafted chain and to exhibit impact resistance. It is advantageous in terms. Among the (meth) acryloyloxyalkylsiloxanes, methacryloyloxyalkylsiloxanes are preferable, and specific examples thereof include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, and γ- Examples thereof include methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, and δ-methacryloyloxybutyldiethoxymethylsilane. Examples of the vinyl siloxane capable of forming the unit represented by the formula (I-2) include vinylmethyldimethoxysilane and vinyltrimethoxysilane.
As the mercaptosiloxane capable of forming the unit represented by -3), γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, γ
-Mercaptopropyldiethoxyethylsilane and the like can be mentioned. The amount of the graft crossing agent (I) used is 0 to 10 mass% in the polyorganosiloxane component.

For the production of this polyorganosiloxane latex, the methods described in, for example, US Pat. Nos. 2,891,920 and 3,294,725 can be used. In the practice of the present invention, an organosiloxane, a cross-linking agent (I) and optionally a mixture of a graft crossing agent (I) are mixed in the presence of a sulfonic acid emulsifier such as an alkylbenzenesulfonic acid or an alkylsulfonic acid, for example, a homogenizer. It is preferably produced by a method of shear mixing with water using the above. Alkylbenzene sulfonic acid is suitable because it acts as an emulsifier of the organosiloxane and at the same time serves as a polymerization initiator. At this time, it is preferable to use a metal salt of alkylbenzene sulfonic acid, a metal salt of alkyl sulfonic acid and the like in combination because it is effective in maintaining the polymer stably during the graft polymerization. After the organosiloxane is polymerized, the polymerization is terminated by neutralizing with an alkaline aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate or the like.

Polyalkyl (meth) constituting the composite rubber
As the acrylate rubber component, the following alkyl (meth) acrylate, polyalkyl (meth) acrylate rubber component crosslinking agent (hereinafter referred to as crosslinking agent (II)) and graft crossing agent (hereinafter referred to as graft crossing agent (II)) are used. Can be synthesized. Examples of the alkyl (meth) acrylate include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and hexyl methacrylate, 2-ethylhexyl methacrylate, and 1-lauryl methacrylate. However, n-butyl acrylate is preferable as the alkyl (meth) acrylate. As the cross-linking agent (II), a polyfunctional (meth) acrylate can be used, and ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate or the like can be used. It can be illustrated as a specific example.

As the graft crossing agent (II), compounds having two kinds of unsaturated groups having different reactivity are used, and examples of such compounds include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like. Among them, allyl methacrylate can also be used as a crosslinking agent. These cross-linking agents (II) and / or graft crossing agents (II) can be used alone or in combination of two or more kinds. These cross-linking agents (II)
The preferred amount of the graft crossing agent (II) used is 0.1 to 10% by mass in the polyalkyl (meth) acrylate rubber component. The method for producing the composite rubber (S) is not particularly limited, but for example, the above-mentioned alkyl (meth) acrylate, cross-linking agent (II) and graft cross-linking agent (II) are added to polyorganosiloxane latex for polymerization. be able to.

The graft copolymer (B) can be prepared by graft-polymerizing a vinyl-based monomer on the composite rubber (S) thus obtained. Examples of the vinyl-based monomer that is graft-polymerized on the composite rubber (S) include monovinyl aromatic hydrocarbons such as styrene and vinyltoluene, monovinylidene aromatic hydrocarbons such as α-methylstyrene, methyl methacrylate, and 2-ethylhexyl methacrylate. Methacrylic acid esters such as; acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate; unsaturated organic acids such as (meth) acrylic acid; epoxy-containing esters such as glycidyl methacrylate; vinyl cyanide such as acrylonitrile and methacrylonitrile. Examples thereof include compounds, which may be used alone or in combination of two or more.

The ratio of the composite rubber (S) to the vinyl monomer used in the graft copolymerization in the graft copolymer (B) is 100% by mass of the graft copolymer (B). Is from 30 to 95% by mass, the dispersibility of the graft copolymer in the resin composition is good,
In addition, the impact strength is increased, which is preferable, and is 40 to 90.
More preferably, it is mass%. The method for producing the graft copolymer (B) is not particularly limited, but an example thereof is a method in which the above vinyl-based monomer is added to the latex-like composite rubber (S) and the radical polymerization is carried out in one step or in multiple steps. For the polymerization, the above-mentioned substances such as an emulsifier, a polymerization initiator and a chain transfer agent can be used. The obtained graft copolymer (B) latex is put into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved, and salted out.
By solidifying, it can be separated and collected as a powder.

The blending ratio of the maleimide copolymer (A) and the graft copolymer (B) in the thermoplastic resin composition of the present invention is not particularly limited, and it can be produced in a wide range. Since the resulting resin composition is excellent in heat resistance and impact resistance, it is preferable to mix the maleimide copolymer (A) in an amount of 20 to 99% by mass when the total amount is 100% by mass.

In addition to the maleimide copolymer (A) and the graft copolymer (B), the thermoplastic resin composition of the present invention may contain other polymers (C) as required. . The other polymer (C) is not particularly limited, and examples thereof include polymethyl methacrylate, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-N-substituted maleimide terpolymer, and styrene-anhydrous. Maleic acid copolymer, styrene-maleic anhydride-N-substituted maleimide terpolymer, polycarbonate resin, polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET resin), polyvinyl chloride, polyethylene, polypropylene and other polyolefins. , Styrene-butadiene-styrene (SB
S), styrene-butadiene (SBR), hydrogenated SB
S, styrene elastomers such as styrene-isoprene-styrene (SIS), various olefin elastomers, various polyester elastomers, polystyrene,
Methyl methacrylate-styrene copolymer (MS resin),
Acrylonitrile-styrene-methyl methacrylate copolymer, polyacetal resin, modified polyphenylene ether (modified PPE resin), ethylene-vinyl acetate copolymer, PPS resin, PES resin, PEEK resin, polyarylate, liquid crystal polyester resin and polyamide resin ( Nylon) and the like,

Preferably, polymethylmethacrylate, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-N-substituted maleimide terpolymer, styrene-maleic anhydride-N-substituted maleimide terpolymer. Coalesce, polycarbonate resin, polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET resin), polyvinyl chloride, polystyrene,
Methyl methacrylate-styrene copolymer (MS resin),
They are an acrylonitrile-styrene-methyl methacrylate copolymer, a modified polyphenylene ether (modified PPE resin), and a polyamide resin, and these can be used alone or in combination of two or more depending on the purpose. In addition, for the purpose of further improving scratch resistance and surface gloss, a resin mainly containing a glutaric anhydride structural unit may be used as the other polymer (C).

When the other polymer (C) is blended, the blending amount thereof is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass in the thermoplastic resin composition. The thermoplastic resin composition of the present invention is a maleimide-based copolymer (A).
And the graft copolymer (B) and, if necessary, the other polymer (C), a Banbury mixer, a roll mill,
It can be obtained by mechanically mixing using a known device such as a twin-screw extruder, and can be appropriately shaped into pellets and used for molding. Further, the resin composition of the present invention may contain a stabilizer, a plasticizer, a lubricant, a flame retardant, a pigment, a dye, a filler, an antistatic agent, etc., if necessary.
For example, stabilizers such as triphenyl phosphite, lubricants such as polyethylene wax and polypropylene wax, flame retardants such as triphenyl phosphate, tricresyl phosphate and other phosphate-based flame retardants, decapromo biphenyl ether, decaprobimo. Brominated flame retardants such as phenyl, titanium oxide, zinc sulfide, zinc oxide, etc. as pigments, glass fiber, asbestos, wollastonite, mica, talc etc. as fillers can be appropriately blended according to the purpose. .

[0031]

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The% and the number of parts in the following examples are based on mass unless otherwise specified. Moreover, various physical properties in each Example and Comparative Example were measured according to the following methods. Izod impact strength Measured according to ASTM D-256 using a 1/4 notched specimen. Vicat softening point temperature It was measured according to ASTM D-1525-91. Molded gloss: A thermoplastic resin composition containing 3 parts of titanium oxide was prepared using an injection molding machine (J85-ELII: Japan Steel Works, Ltd.) with a cylinder set temperature of 230 ° C., a mold temperature of 60 ° C., and an injection speed of 50%. 100 mm x 100 m under the conditions
A m × 3 mm plate was molded. The surface gloss of the obtained white colored molded plate was measured according to the method of ASTM D-523-62T (60 degree specular gloss).

A molded plate was prepared under the same conditions as for the thermoplastic resin composition to which 0.8 part of the coloring carbon black was added. The obtained black colored molded plate was subjected to hue measurement (L * measurement) in accordance with JIS Z8729. Using a sunshine weatherometer (WEL-SUN-DCH type manufactured by Suga Test Instruments Co., Ltd.), the molded plate obtained with weather resistance was black panel temperature 63 ° C., water 12 minutes, and dried 60.
The cycle of minutes exposed for 1000 hours. Then, the gloss of the molded plate after the exposure was measured. Molded under the same conditions, except that titanium oxide was not added, using an injection molding machine used for thermal decomposition at a set temperature of 300 ° C.
The number of silver streaks generated on the surface was measured.

Reference Example 1: Maleimide type copolymer (A-
1) Production A pressure resistant polymerization kettle equipped with a stirrer was charged with 200 parts of distilled water, 0.1 part of a copolymer consisting of methyl methacrylate and 2-sulfoethyl sodium methacrylate, 0.3 parts of sodium sulfate, and then 25 parts of methyl methacrylate. Styrene 30 parts α-methylstyrene 25 parts N-phenylmaleimide 20 parts n-octyl mercaptan 0.25 parts Azobisisobutyronitrile 0.2 parts A monomer mixture is charged and stirred at room temperature for 2
After bubbling nitrogen for 0 minutes to remove oxygen, the internal temperature 8
Suspension polymerization was carried out at 0 ° C for 3 hours, then the temperature was further raised to 120 ° C, and the temperature was maintained for 30 minutes, followed by cooling, filtration,
It was washed with water and dried to obtain a beaded maleimide copolymer (A-1) having an average particle size of about 200 μm and a mass average molecular weight of 103,000.

Reference Examples 2 to 10: Production of Maleimide Copolymers (A-2) to (A-10) In the examples described in Reference Example 1, the type and amount of the monomer mixture used are as shown in Table 1. This was changed to obtain bead-shaped maleimide copolymers (A-2) to (A-10).

[0035]

[Table 1]

Reference Example 11: Production of polyorganosiloxane latex (L-1) Octamethylcyclotetrasiloxane 98 parts γ-methacryloyloxypropyldimethoxymethylsilane 2 parts were mixed to obtain 100 parts of a siloxane-based mixture. 300 parts of ion-exchanged water in which 0.67 part of sodium dodecylbenzenesulfonate was dissolved was added to this, and the mixture was stirred with a homomixer at 10,000 rpm for 2 minutes, and then passed through a homogenizer once at a pressure of 200 MPa to stabilize. A premixed organosiloxane latex was obtained. On the other hand, 10 parts of dodecylbenzenesulfonic acid and 90 parts of ion-exchanged water were injected into a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirring device to prepare a 10% aqueous solution of dodecylbenzenesulfonic acid. . With this aqueous solution heated to 85 ° C.,
The premixed organosiloxane latex was added dropwise over 4 hours, and the temperature was maintained for 1 hour after completion of the addition, followed by cooling.
The reaction was then neutralized with aqueous sodium hydroxide solution. The polyorganosiloxane (L-1) thus obtained
The latex was dried at 170 ° C. for 30 minutes to determine the solid content, which was 17.7%. The weight average particle diameter of the polyorganosiloxane (L-1) in the latex was 0.05 μm.

Reference Example 12: Preparation of polyorganosiloxane (L-2) latex Octamethylcyclotetrasiloxane 97.5 parts γ-methacryloyloxypropyldimethoxymethylsilane 0.5 parts Tetraethoxysilane 2 parts are mixed to obtain a siloxane system. 100 parts of mixture are obtained. An aqueous solution consisting of 1 part of dodecylbenzene sulfonic acid, 1 part of sodium dodecylbenzene sulfonate, and 200 parts of ion-exchanged water was added to this, and the mixture was mixed with a homomixer at 10,000.
After stirring for 2 minutes at rotation / minute, add 200 to the homogenizer.
It was passed once under a pressure of MPa to obtain a stable premixed organosiloxane latex. The premixed organosiloxane latex was placed in a reactor equipped with a cooling tube, a jacket heater and a stirrer, and mixed with stirring to 80
After heating at ℃ for 5 hours, cool to about 20 ℃,
Left for hours. Then, the reaction product was neutralized to pH 7.0 with a caustic soda aqueous solution to complete the polymerization. The polyorganosiloxane (L-2) latex thus obtained was dried at 170 ° C. for 30 minutes to obtain a solid content, which was 3
It was 6.5%. The weight average particle diameter of the polyorganosiloxane (L-2) in the latex is 0.16 μm.
Met.

Reference Example 13: Production of composite rubber (S-1) and graft copolymer (B-1) Reference Example 11 was placed in a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirrer. 8 parts of polyorganosiloxane (L-1, solid content) produced in (1) 0.2 parts of Emal NC-35 (polyoxyethylene alkyl phenyl ether sulfate; manufactured by Kao Corporation) was collected, and 200 parts of ion-exchanged water (( L-1) containing water) and mixed, and then mixed with butyl acrylate 42 parts allyl methacrylate 0.3 parts 1,3-butylene glycol dimethacrylate 0.1 parts t-butyl hydroperoxide 0.11 parts. Was added.

By passing a nitrogen stream through this reactor, the atmosphere was replaced with nitrogen, and the temperature was raised to 60.degree. When the internal liquid temperature reached 60 ° C., an aqueous solution containing ferrous sulfate 0.000075 parts ethylenediaminetetraacetic acid disodium salt 0.000225 parts Rongalit 0.2 parts ion-exchanged water 10 parts was added to perform radical polymerization. Started.
The liquid temperature rose to 78 ° C. due to the polymerization of the acrylate component. This state was maintained for 1 hour to complete the polymerization of the acrylate component to obtain a latex of a composite rubber (S-1) of polyorganosiloxane (L-1) and butyl acrylate rubber. The mass average particle diameter of this composite rubber (S-1) was 0.11 μm.

After the liquid temperature inside the reactor was lowered to 70 ° C., an aqueous solution consisting of 0.25 parts of Rongalit and 10 parts of ion-exchanged water was added, and then 2.5 parts of acrylonitrile 2.5 parts of styrene 7.5 parts of t-butyl hydroper. A mixed solution of 0.05 part of oxide was added dropwise over 2 hours to carry out polymerization. After the dropping, the temperature of 60 ° C. was maintained for 1 hour, and then ferrous sulfate 0.001 part ethylenediaminetetraacetic acid disodium salt 0.003 part Rongalit 0.2 part Emal NC-35 (manufactured by Kao Corporation) 0.2 parts ion-exchanged water 10 parts aqueous solution was added, and then

A mixed solution of 10 parts of acrylonitrile, 30 parts of styrene, and 0.2 parts of t-butyl hydroperoxide was added dropwise over 2 hours for polymerization. After the dropping is completed, the temperature of 60 ° C. is maintained for 0.5 hours, and then 0.05 part of cumene hydroperoxide is added,

Further, the temperature of 60 ° C. was maintained for 0.5 hour and then cooled. To this latex, 0.5 part of latemul ASK (alkenylsuccinic acid dipotassium salt; manufactured by Kao Corporation) was added, and acrylonitrile and styrene were grafted to a composite rubber composed of polyorganosiloxane (L-1) and butyl acrylate rubber. A latex of the polymerized graft copolymer (B-1) was obtained. The weight average particle diameter of the graft copolymer (B-1) in the latex was 0.12 μm.
It was m. Next, 150 parts of an aqueous solution in which calcium acetate was dissolved at a ratio of 1% was heated to 60 ° C. and stirred. 100 parts of the latex of the graft copolymer (B-1) was gradually dropped into this and coagulated. Next, the precipitate is separated, washed, and then centrifuged (Domestic Centrifuge Co., Ltd .; H-130E).
Was dehydrated for 2 minutes under the condition of 1800 rpm. Subsequently, it dried at 85 degreeC for 24 hours, and obtained the graft copolymer (B-1). Further, the graft copolymer (B-
The acetone insoluble content in 1) was 85%.

Reference Example 14: Production of composite rubber (S-2) and graft copolymer (B-2) Reference Example 12 was placed in a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirrer. Polyorganosiloxane latex (L-2, solid content) obtained in 7.8 parts 0.2 parts of sodium N-lauroyl sarcosinate was mixed, and 200 parts of distilled water (including water in (L-2))
Was added and mixed, and then a mixture of butyl acrylate 47.2 parts allyl methacrylate 0.27 parts 1,3-butylene glycol dimethacrylate 0.07 parts cumene hydroperoxide 0.11 parts was added. The atmosphere was replaced with nitrogen by passing a nitrogen stream through this reactor, and the temperature was raised to 60 ° C. When the internal liquid temperature reached 60 ° C, ferrous sulfate 0.00006 part ethylenediaminetetraacetic acid disodium salt 0.0002 part rongalit 0.16 part distilled water 6.7 parts

An aqueous solution consisting of was added to initiate radical polymerization. The liquid temperature was raised to 78 ° C. by the polymerization of the acrylate component. This state is maintained for 1 hour to complete the polymerization of the acrylate component, and the composite rubber (S of polyorganosiloxane (L-2) and butyl acrylate rubber (S
-2) A latex was obtained. Obtained composite rubber (S-2)
The mass average particle size of was 0.25 μm. Next, after the liquid temperature inside the reactor dropped to 60 ° C., an aqueous solution containing 0.4 parts of Rongalit and 6.7 parts of distilled water was added, and then

A mixed solution of 6.2 parts of acrylonitrile, 18.8 parts of styrene and 0.11 part of cumene hydroperoxide was added dropwise over 2 hours for polymerization. After the dropping, the temperature of 60 ° C was maintained for 1 hour, and then an aqueous solution of ferrous sulfate 0.00013 part ethylenediaminetetraacetic acid disodium salt 0.0004 part Rongalit 0.15 part distilled water 6.7 parts was added. Then, a mixed solution of 5 parts of acrylonitrile, 15 parts of styrene and 0.09 part of cumene hydroperoxide was added dropwise over 2 hours for polymerization. After completion of dropping, the temperature of 60 ° C. was maintained for 1 hour and then cooled, and acrylonitrile and styrene were graft-polymerized to the composite rubber (S-2) composed of polyorganosiloxane (L-2) and butyl acrylate rubber. A latex of the graft copolymer (B-2) was obtained. Next, 100 parts of an aqueous solution in which aluminum sulfate was dissolved at a ratio of 5 mass% was added at 60 ° C
It was heated to and stirred. Graft copolymer (B-
2) 100 parts of latex was gradually dropped to coagulate. Next, the precipitate was separated, washed and dried to obtain a powdery graft copolymer (B-2). Graft copolymer (B-
The acetone insoluble content in 2) was 87%.

Reference Example 15: Production of composite rubber (S-3) and graft copolymer (B-3) A polyorganosiloxane was placed in a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirrer. Latex (L-2, solid content) 30 parts Ion-exchanged water (including water in (L-2)) 242.9 parts was added, and after nitrogen substitution, the temperature was raised to 50 ° C. and n-butyl acrylate 37. 5 parts Allyl methacrylate 2.5 parts Mixture of t-butyl hydroperoxide 0.3 parts was added and stirred at room temperature for 30 minutes. Then, an aqueous solution consisting of ferrous sulfate heptahydrate 0.0003 parts ethylenediaminetetraacetic acid disodium salt 0.001 part Rongalit 0.17 parts ion-exchanged water 5 parts is added to initiate radical polymerization, and then the internal temperature 70 Polymerization was maintained at 2 ° C. for 2 hours to complete the polymerization of acrylate to obtain a composite rubber (S-3) latex.
The weight average particle diameter of this composite rubber (S-3) was 0.19 μm.
It was m.

Subsequently, to this composite rubber (S-3), a mixture of 9 parts of acrylonitrile, 21 parts of styrene and 0.3 parts of t-butyl hydroperoxide was added dropwise at an internal temperature of 70 ° C. for 45 minutes, and then 70 ° C. Hold for 4 hours in the composite rubber (S-
Graft polymerization to 3) was completed. This graft copolymer (B-3) latex was put into an aqueous solution of the same amount of 12% calcium chloride at 60 ° C. with stirring, and then 80
It was solidified by holding at 5 ° C. for 5 minutes and then at 95 ° C. for 5 minutes. Then, the precipitate was separated, washed, and then dehydrated. Subsequently, it dried at 85 degreeC for 24 hours, and obtained the graft copolymer (B-3). The content of acetone insoluble in this graft copolymer (B-3) was 93%.

Reference Example 16: Graft copolymer (B-4)
In Production Reference Example 15 of the above, polymerization and coagulation recovery were carried out in the same manner except that the composite rubber (S-3) was used as a monomer for graft polymerization and acrylonitrile and styrene were all methyl methacrylate. Coalescence (B
-4) was obtained. The content of acetone insoluble in this graft copolymer (B-4) was 83%.

Reference Example 17: Graft copolymer (B-5)
By a known emulsion polymerization, 50 parts of polybutadiene rubber having a mass average particle diameter of 0.3 μm was added to 15 parts of acrylonitrile.
Parts and styrene 35 parts of the monomer mixture was graft-polymerized to obtain a diene rubber-based graft copolymer (B-5).

Reference Example 18: Graft copolymer (B-6)
By a known emulsion polymerization, 50 parts of polybutadiene rubber having a mass average particle diameter of 0.2 μm was mixed with 3 parts of methyl methacrylate.
5 parts and styrene 12.5 parts, acrylonitrile 2.
A diene rubber-based graft copolymer (B-6) obtained by graft-polymerizing a monomer mixture consisting of 5 parts was obtained.

Reference Example 19: Production of other polymer (C-1) By known suspension polymerization, 99 parts of methyl methacrylate,
Weight average molecular weight 7 consisting of 1 part of methyl acrylate
1,000, a bead-shaped acrylic copolymer (C-
1) was obtained.

Examples 1-10, Comparative Examples 1-7: Reference Example 1
Maleimide copolymer (A-1) produced in
(A-10), graft copolymers (B-1) to (B-6) obtained in Reference Examples 13 to 18, and, if necessary, other copolymers (C-1) obtained in Reference Example 19 As shown in Table 2 so as to make a total of 100 parts, and 0.4 parts of ethylenebisstearylamide and 0.4 part of barium stearate were blended and blended in a Henschel mixer. (Manufactured by Japan Steel Works, Ltd., TEX-30
α), melt-kneaded at a cylinder temperature of 250 ° C., and shaped into pellets. After drying the obtained pellets, they are supplied to an injection molding machine (J85ELII type manufactured by Japan Steel Works, Ltd.) and injection-molded at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. to obtain various test pieces and physical properties. Was evaluated. Table 2 shows the evaluation results of these resin compositions.

[0053]

[Table 2]

As is clear from Table 2, Examples 1-10
The thermoplastic resin composition (1) had a high Izod impact strength, a Vicat softening point temperature, a high thermal decomposition resistance, a good gloss and colorability of the molded appearance, and a good weather resistance due to accelerated exposure. On the other hand, the thermoplastic resin compositions of Comparative Examples 1 to 7 were inferior in any item of Izod impact strength, heat resistance, thermal decomposition resistance, molding appearance such as gloss and colorability, and weather resistance. Further, from Examples 1 and 3, the maleimide-based monomer used in the maleimide-based copolymer was N-.
In the case of phenylmaleimide, the balance between Izod impact strength and Vicat softening point temperature was excellent.
Further, from Examples 1 and 8 to 9, the particle diameter of the composite rubber used in the graft copolymer is 0.03 to 0.15 μm.
In the range of 1, the L * value was low and the coloring property was excellent.
In particular, the thermoplastic resin compositions of Examples 1, 2, and 7 can express a balance of Izod impact strength, heat resistance, thermal decomposition resistance, molding appearance, and weather resistance at a high level that has hitherto been unknown.

[0055]

As described in detail above, according to the present invention, a good molded resin appearance, high heat resistance and thermal decomposition resistance can be obtained, and further, a high level of mechanical strength such as impact resistance can be obtained. It is possible to provide a thermoplastic resin composition having weather resistance. In particular, the balance of impact resistance, heat resistance, thermal decomposition resistance, molding appearance and weather resistance is extremely excellent as compared with conventionally known rubber-modified thermoplastic resin compositions, and the thermoplastic resin composition of the present invention Products are extremely valuable as various industrial materials.

[Brief description of drawings]

FIG. 1 is a compositional triangular coordinate showing a blending ratio of a maleimide copolymer (A) in a thermoplastic resin composition of the present invention.

Claims (4)

[Claims] 1. N-substituted maleimide, alkyl (meth)
In a triangular coordinate composed of an acrylate unit and another copolymerizable monomer, point a (N-substituted maleimide 1% by mass, alkyl (meth) acrylate unit 1% by mass, other copolymerizable monomer) 98% by mass), point b (1% by mass of N-substituted maleimide, 30% by mass of alkyl (meth) acrylate unit, 69% by mass of other copolymerizable monomer), c
Dots (71% by mass of N-substituted maleimide, alkyl (meth))
Acrylate unit 29% by weight, other copolymerizable monomer 0% by weight, and d point (N-substituted maleimide 99% by weight, alkyl (meth) acrylate unit 1% by weight, other copolymerizable unit amount. (1% by mass) (1%) for a maleimide copolymer (A) having a monomer unit composition and a polyorganosiloxane / alkyl (meth) acrylate composite rubber (S) in a region formed by connecting 4 points of the body. Alternatively, a thermoplastic resin composition containing a graft copolymer (B) obtained by graft-polymerizing two or more vinyl monomers. 2. The thermoplastic resin composition according to claim 1, wherein the N-substituted maleimide is N-phenylmaleimide. 3. The mass average particle diameter of the polyorganosiloxane / alkyl (meth) acrylate composite rubber (S) used in the graft copolymer (B) is 0.01 to 1.0 μm.
The thermoplastic resin composition according to claim 1, which is m. 4. The mass average particle diameter of the polyorganosiloxane / alkyl (meth) acrylate composite rubber (S) used in the graft copolymer (B) is 0.03 to 0.15.
The thermoplastic resin composition according to claim 1, which has a thickness of μm.