JP2003277567A - Thermoplastic resin composition - Google Patents

Abstract

[57] [Summary] [PROBLEMS] To provide a resin material that simultaneously satisfies the impact resistance, molding appearance such as coloring and gloss of a maleimide resin composition modified with a rubber-like polymer, and a high level of weather resistance. Develop. SOLUTION: At a triangular coordinate composed of an N-substituted maleimide unit, an alkyl (meth) acrylate unit, and another copolymerizable monomer, a point (1 mass% of N-substituted maleimide unit, alkyl (meta) Acrylate unit 4
5% by mass, 54% by mass of other monomers that can be copolymerized), b point (N-substituted maleimide unit 1% by mass, alkyl (meth))
99% by mass of acrylate units, 0% by mass of other copolymerizable monomers), and point c (55% by mass of N-substituted maleimide units, 45% by mass of alkyl (meth) acrylate units,
Maleimide copolymer (A) and a polyorganosiloxane / alkyl (meth) acrylate having a monomer unit composition in a region formed by connecting three points of other copolymerizable monomers (0% by mass) A thermoplastic resin composition comprising a graft copolymer (B) obtained by graft-polymerizing one or more vinyl monomers to the composite rubber (S).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to heat resistance, weather resistance,
The present invention relates to a maleimide resin composition having excellent impact resistance, and more particularly to a maleimide resin composition containing a maleimide copolymer and a polyorganosiloxane / alkyl (meth) acrylate composite rubber-based graft copolymer.

[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. 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 used in such a field, a matrix of a maleimide type copolymer obtained by copolymerizing an N-substituted maleimide compound having excellent heat resistance and impact resistance with an aromatic vinyl compound and a vinyl cyanide compound is used. 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. In addition, JP-A-2000-
Japanese Patent No. 143929 proposes a transparent thermoplastic resin composition obtained by adding a specific maleimide copolymer and a rubber-modified thermoplastic resin having a refractive index close to that of the specific maleimide copolymer.

However, conventional resin materials composed of a maleimide copolymer modified with a rubber-like polymer cannot obtain the high level of weather resistance required in recent years, and further, the coloring property and gloss are not achieved. The molding appearance was also insufficient.

[0005]

The object of the present invention is to simultaneously provide a maleimide resin composition modified with a rubber-like polymer with impact resistance, molding appearance such as colorability and gloss, and high level weather resistance. It is to develop a resin material that satisfies the requirements.

[0006]

Means for Solving the Problems As a result of intensive studies for achieving the above object, the present inventors have found that a thermoplastic resin composition excellent in heat resistance, impact resistance, weather resistance and molding appearance is obtained. Is a maleimide-based polymer having a specific composition and a graft copolymer (hereinafter referred to as a graft copolymer) obtained by graft-polymerizing a vinyl-based monomer on a composite rubber composed of a polyorganosiloxane and a polyalkyl (meth) acrylate rubber. The present invention has been completed by finding that a thermoplastic resin composition having excellent heat resistance and impact resistance, as well as excellent molding appearance and weather resistance can be obtained by blending it with a copolymer.

That is, according to the present invention, the N-
On a triangular coordinate composed of a substituted maleimide unit, an alkyl (meth) acrylate unit, and another copolymerizable monomer, point a (N-substituted maleimide unit 1% by mass, alkyl (meth) acrylate unit 45% by mass) , 54% by weight of other copolymerizable monomer), point b (1% by weight of N-substituted maleimide unit, alkyl (meth) acrylate unit 9)
9% by weight, 0% by weight of other copolymerizable monomer), and c
A monomer in a region formed by connecting three points (55% by mass of N-substituted maleimide unit, 45% by mass of alkyl (meth) acrylate unit and 0% by mass of other copolymerizable monomer). A graft copolymer obtained by graft-polymerizing one or more vinyl monomers to the maleimide-based copolymer (A) having a unit composition and the polyorganosiloxane / alkyl (meth) acrylate composite rubber (S) ( B) and a thermoplastic resin composition containing the same.

[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 other copolymerizable monomers as necessary. And a copolymer thereof. The N-substituted maleimide is not particularly limited, and examples thereof include N-methyl maleimide, N-ethyl maleimide, N-n-propyl maleimide, N-i-propyl maleimide, N-n-butyl maleimide, N-i- Butyl maleimide, N-tert-butyl maleimide, N
-Cyclohexylmaleimide, etc., N-cycloalkylmaleimide, N-phenylmaleimide represented by the following general formula, N-arylmaleimide such as N-substituted phenylmaleimide: N-aralkylmaleimide, and one of these 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,
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, pendyl methacrylate, phenyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-acrylic acid
-Propyl, 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,
Such as ethyl acrylate. These alkyl (meth)
The acrylate compound may be used alone or in combination of two or more.

Other copolymerizable monomers that can be used in the maleimide copolymer (A) are not particularly limited, but for example, aromatic vinyl compounds, vinyl cyanide compounds and the like can be used. Group vinyl compounds are preferred. Specific examples of the aromatic vinyl compound include monovinyl aromatic hydrocarbon and monovinylidene aromatic hydrocarbon. Monovinyl aromatic hydrocarbons include styrene, o-, m- or p-
Methylstyrene (o-, m- or p-vinyltoluene), pt-butylstyrene, o-, m- or p-chlorostyrene, 2,4-dipromostyrene, also as monovinylidene aromatic hydrocarbons. Examples thereof include α-methylstyrene and α-ethylstyrene. 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.

As the vinyl cyanide compound, acrylonitrile, methacrylonitrile, ethacrylonitrile,
Examples thereof include maleonitrile and fumaronitrile, and of these, 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) used in the present invention has a point a (N-substituted maleimide unit 1% by mass, alkyl (meth)) in the triangular coordinates shown in FIG.
Acrylate unit 45% by mass, other copolymerizable monomer 54% by mass), point b (N-substituted maleimide unit 1% by mass, alkyl (meth) acrylate unit 99% by mass, other copolymerizable unit amount) Body 0% by mass) and point c (N-substituted maleimide unit 55% by mass, alkyl (meth) acrylate unit 45% by mass, other copolymerizable monomer 0% by mass). Used in a composition within a triangular region, preferably (N-substituted maleimide unit 2.5% by mass, alkyl (meth) acrylate unit 50
Mass%, other copolymerizable monomer 47.5 mass%),
(N-substituted maleimide unit 2.5% by mass, alkyl (meth) acrylate unit 95% by mass, other copolymerizable monomer 2.5% by mass), and (N-substituted maleimide unit 4
7.5% by mass, 50 alkyl (meth) acrylate units
% By mass, and 2.5% by mass of other copolymerizable monomer) within a triangular region formed by connecting three points.

Preferably, (N-substituted maleimide unit 5% by mass, alkyl (meth) acrylate unit 55% by mass,
Copolymerizable other monomer 40% by mass), (N-substituted maleimide unit 5% by mass, alkyl (meth) acrylate unit 90% by mass, copolymerizable other monomer 5% by mass), and ( Within the range of a triangular region formed by connecting three points of N-substituted maleimide unit 40% by mass, alkyl (meth) acrylate unit 55% by mass, and another copolymerizable monomer 5% by mass. . It is preferable to use the maleimide-based copolymer (A) having such a composition because it can improve the balance of heat resistance, weather resistance and impact resistance of the thermoplastic resin.

The maleimide copolymer (A) used in the present invention can be produced by a known polymerization method such as emulsion polymerization, suspension polymerization and bulk polymerization. For example, as a production method by the suspension polymerization method, benzoyl peroxide, t-butyl peroxybenzoate,
Organic oxides such as lauroyl peroxide, 1,1 '
-Azobiscyclohexane-1-carbonitrile, 1,
Radical generators such as azo compounds such as 1′-azobisisobutyronitrile, mercaptans such as t-dodecyl mercaptan and octyl mercaptan as a molecular weight regulator, and (meth) acryl as a suspension stabilizer (dispersing agent). Copolymer of methyl acid and sodium salt of 2-sulfoethyl methacrylate, poorly soluble phosphates such as hydroxyabatite, tricalcium phosphate, magnesium phosphate, etc., inorganics such as barium sulfate, calcium magnesium sulfate, magnesium carbonate, etc. The polymerization reaction may be carried out according to a known method using a compound or a protective colloid agent such as polyvinyl alcohol or methyl cellulose.

Further specific examples of the production of the maleimide-based copolymer (A) will be given. For example, a polymerization catalyst and a molecular weight modifier are dissolved in one or two other monomers except N-substituted maleimide. , A method of conducting polymerization by adding the solution to a reaction vessel containing water, a suspension stabilizer and the remaining monomer, or in a reaction vessel, a polymerization catalyst, a molecular weight modifier,
It is possible to employ a method in which the suspension stabilizer is added to water and then the monomers are added simultaneously or in portions to carry out the polymerization. The particle size of the maleimide-based copolymer (A) is not particularly limited, but when produced by suspension polymerization, the weight average particle size is 10 to 10.
From the viewpoint of kneading operability with the graft copolymer (B), it is preferable to adjust the dispersion conditions such as the stirring state so as to obtain 8000 μm, preferably 50 to 5000 μm. The molecular weight of the maleimide-based copolymer (A) of the present invention is not particularly limited, but the mass average molecular weight is 10,000 to 300, because the resulting thermoplastic resin composition has an excellent balance of impact resistance and molding processability. It is preferably in the range of 000, more preferably 20,000 to 20.
It is in the range of 10,000.

The graft copolymer (B) used in the present invention is a composite rubber composed of a polyorganosiloxane component and a polyalkyl (meth) acrylate rubber component ((S), hereinafter simply referred to as composite rubber). One or two or more vinyl monomers are 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 cannot be obtained. A siloxane component and a polyalkyl (meth) acrylate rubber component are combined to give a molded article having excellent impact resistance, mechanical strength, and molding appearance.

Composite rubber (S) of graft copolymer (B)
May have any composition range of the polyorganosiloxane component and the polyalkyl (meth) acrylate rubber component, but is preferably polyorganosiloxane because the resin composition has good impact resistance and good molding appearance. The components are in the range of 5 to 80% 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 preferably in the range of 0.01 to 1.0 μm, more preferably 0.03 to 1.0, since the obtained resin composition has good colorability. 0.
It is in the range of 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 a cross-linking agent for organosiloxane and polyorganosiloxane shown below (hereinafter referred to as cross-linking agent (I)). A graft crossing agent for organosiloxane (hereinafter referred to as a graph and crossing agent (I)) can be used in combination.

As the above-mentioned organosiloxane, various cyclic compounds having three or more membered rings can be used, and those having 3 to 6 membered rings are preferably used. Examples of 3- to 6-membered organosiloxanes include hexamethylcyclotrisiloxane,
Examples thereof include octamethylcyclotetrasiloxane, decamethylcyclopentanesiloxane, dodecamethylcyclohexanetetrasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane and octaphenylcyclotetrasiloxane. These may be used alone or in combination of two or more. The amount of the organosiloxane used is 60% by mass or more in the polyorganosiloxane component,
It is preferably at least mass%.

As the cross-linking agent (I), a trifunctional (trialkoxysilane) or tetrafunctional (tetraalkoxysilane) silane compound is used, and trimethoxysilane, triethoxyphenylsilane, tetramethoxysilane or tetraethoxy is used. Examples thereof include silane, tetra-n-propoxysilane, and tetrabutoxysilane. Among these, a tetrafunctional silane compound is 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.

As the graft crossing agent, the following formula (I-1 to
3)

[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, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, δ
-Methacryloyloxybutyldiethoxymethylsilane and the like. Examples of the vinyl siloxane capable of forming the unit represented by the formula (I-2) include vinylmethyldimethoxysilane and vinyltrimethoxysilane, and the unit represented by the formula (I-3) can be formed. Examples of the mercaptosiloxane may include γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyldiethoxyethylsilane. Graft crossing agent (I)
Is used in the polyorganosiloxane component from 0 to 10 mass.
%.

This polyorganosiloxane latex is disclosed, for example, in US Pat.
It can be obtained by the method described in the specification of 294725 or the like. In the present invention, the organosiloxane, the cross-linking agent (I) and, if desired, the graft crossing agent (I) are mixed in the presence of a sulfonic acid-based emulsifier such as alkylbenzene sulfonic acid or alkyl sulfonic acid with a homogenizer or the like. It is preferably produced by a method of shear mixing with water. 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) that constitutes the composite rubber
As the acrylate rubber component, the following alkyl (meth) acrylate, polyalkyl (meth) acrylate rubber component cross-linking agent (hereinafter referred to as cross-linking agent (II)) and the same graft crossing agent (hereinafter referred to as graft crossing agent (II)) are used. Can be used to synthesize. Examples of alkyl (meth) acrylates include methyl acrylate, ethyl acrylate,
n-propyl acrylate, n-butyl acrylate,
Examples thereof include alkyl acrylates such as 2-ethylhexyl acrylate and hexyl methacrylates, alkyl methacrylates such as 2-ethylhexyl methacrylate and 1-lauryl methacrylate, and n-butyl acrylate is preferably used as the alkyl (meth) acrylate. A polyfunctional (meth) acrylate can be used as the cross-linking agent (II), and ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate,
Specific examples thereof include 1,4-butylene glycol dimethacrylate.

As the graft crossing agent (II), a compound having two kinds of unsaturated groups having different reactivities is used, and examples of such a compound 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. Also, a cross-linking agent (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, methacrylonitrile, etc. A compound etc. can be mentioned, These are used individually or in combination of 2 or more types.

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) when the composite rubber (S) is used. 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 preferably 40 to
It is 90% by mass. The method for producing the graft copolymer (B) is not particularly limited, but as an example, the graft copolymer (B) is obtained by adding the above vinyl-based monomer to the latex-like composite rubber (S) and performing radical polymerization in one step or in multiple steps. At this time, as the emulsifier, polymerization initiator and chain transfer agent that can be used, those mentioned above can be used. Obtained graft copolymer (B)
The latex can be separated and collected in the form of powder by adding it to hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved and salting out and coagulating.

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-based copolymer (A) and the graft copolymer (B), the thermoplastic resin composition of the present invention can be blended with other polymers (C) as required.

The other polymer (C) is not particularly limited, and examples thereof include polymethylmethacrylate, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-N-substituted maleimide terpolymer, Styrene-maleic anhydride copolymer, styrene-maleic anhydride-N-substituted maleimide terpolymer, polycarbonate resin, polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET resin), polyvinyl chloride, polyethylene, polypropylene Polyolefins such as 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.

Of these, polymethylmethacrylate and acrylonitrile-styrene copolymer (AS) are preferable.
Resin), acrylonitrile-styrene-N-substituted maleimide terpolymer, styrene-maleic anhydride-N-substituted maleimide terpolymer, polycarbonate resin, polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET resin) , Polyvinyl chloride, polystyrene, methyl methacrylate-styrene copolymer (MS resin), acrylonitrile-styrene-methyl methacrylate copolymer, modified polyphenylene ether (modified PPE resin), and polyamide resin, depending on the purpose. Can be used alone or in combination of two or more. In addition, a resin containing a glutaric anhydride structural unit as a main component may be used as the other polymer (C) for the purpose of further improving scratch resistance and surface gloss. When blending the other polymer (C), the blending amount thereof is preferably 0 to 50 parts by mass in the thermoplastic resin composition,
More preferably, it is 0 to 30 parts by mass.

The thermoplastic resin composition of the present invention comprises a maleimide copolymer (A) and a graft copolymer (B).
If necessary, it can be obtained by mechanically mixing the other polymer (C) with a known device such as a Banbury mixer, a roll mill, a twin-screw extruder, etc., and appropriately shape this into a pellet form. And can be 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. Examples of stabilizers that can be used include triphenyl phosphite and the like, lubricants such as polyethylene wax and polypropylene wax, and flame retardants such as triphenyl phosphate and phosphate-based flame retardants such as tricresyl phosphate and decapromo. Examples include brominated flame retardants such as biphenyl ether and decapro bimophenyl, pigments such as titanium oxide, zinc sulfide and zinc oxide, and fillers such as glass fiber, asbestos, wollastonite, mica and talc. it can.

[0033]

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. Various physical properties in Examples and Comparative Examples 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 used, using an injection molding machine "J85-ELII" manufactured by Japan Steel Works, Ltd., to set a cylinder temperature of 230 ° C, a mold temperature of 60 ° C, and an injection speed. 100 mm x 100 m under 50% condition
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 thermoplastic resin composition to which 0.8 part of coloring carbon black was added was prepared as an evaluation sample under the same conditions as described above. 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 molding 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 and ΔE value (color difference from the unexposed sample) of the exposed orthoped plate were measured.

Reference Example 1: Production of Maleimide Copolymer (A-1) In a pressure resistant polymerization kettle equipped with a stirrer, 200 parts of distilled water 0.1 part of a copolymer composed of methyl methacrylate and 2-sulfoethyl sodium methacrylate. 0.3 parts of sodium sulfate was charged, methyl methacrylate 75 parts Styrene 5 parts α-methylstyrene 5 parts N-phenylmaleimide 15 parts n-octyl mercaptan 0.25 parts Azobisisobutyronitrile 0.2 parts Charge the body mixture and stir 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,
After washing with water and drying, a bead-shaped maleimide copolymer (A-1) having an average particle size of about 200 μm and a mass average molecular weight of 105,000 was obtained.

Reference Examples 2 to 8: Production of Maleimide Copolymers (A-2) to (A-8) In the examples described in Reference Example 1, the type and amount of the monomer mixture used are shown in Table 1. Were changed as described above to obtain bead-shaped maleimide copolymers (A-2) to (A-8).

[0037]

[Table 1]

Reference Example 9: 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 10: Production 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 11: Production of Composite Rubber (S-1) and Graft Copolymer (B-1) Reference Example 9 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. 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 reaches 60 ° C,

Ferrous sulfate 0.000075 parts Ethylenediaminetetraacetic acid disodium salt 0.000225 parts Rongalite 0.2 parts Ion-exchanged water An aqueous solution of 10 parts was added to initiate radical polymerization.
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 temperature of the liquid inside the reactor dropped to 70 ° C., an aqueous solution containing 0.25 parts of Rongalit and 10 parts of ion-exchanged water was added, and then,

A mixed solution of acrylonitrile (2.5 parts), styrene (7.5 parts) and t-butyl hydroperoxide (0.05 parts) was added dropwise over 2 hours for 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) An aqueous solution consisting of 0.2 parts of ion-exchanged water of 10 parts 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 maintaining the temperature of 60 ° C. for 0.5 hours after the completion of dropping

Cumene hydroperoxide (0.05 parts) was added, and the temperature of 60 ° C. was maintained for 0.5 hours and then cooled. To this latex, 0.5 part of Latemur ASK (alkenyl succinic acid dipotassium salt; manufactured by Kao Corporation) was added, and acrylonitrile and styrene were grafted onto 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 12 Production of Composite Rubber (S-2) and Graft Copolymer (B-2) Reference Example 10 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.

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 0.00006 parts ethylenediaminetetraacetic acid disodium salt 0.0002 parts Rongalit 0.16 parts distilled water 6.7 parts was added, and radicals were added. Polymerization was initiated. The liquid temperature was raised to 78 ° C. by the polymerization of the acrylate component. This state was maintained for 1 hour to complete the polymerization of the acrylate component to obtain a composite rubber (S-2) latex of polyorganosiloxane (L-2) and butyl acrylate rubber. The mass average particle diameter of the obtained composite rubber (S-2) was 0.25 μm. The liquid temperature inside the reactor is 6
After the temperature was lowered to 0 ° C., an aqueous solution containing 0.4 part 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 for 2 hours. It was dripped over and polymerized. After the dropping is completed, the temperature of 60 ° C. is maintained for 1 hour,

Ferrous sulfate 0.00013 parts Ethylenediaminetetraacetic acid disodium salt 0.0004 parts Rongalit 0.15 parts Distilled water 6.7 parts Aqueous solution was added, and then acrylonitrile 5 parts Styrene 15 parts Cumene hydroperoxide A mixed solution of 0.09 parts 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). The acetone insoluble content in the graft copolymer (B-2) was 87%.

Reference Example 13: Production of Composite Rubber (S-3) and Graft Copolymer (B-3) 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). In addition, the acetone insoluble content in the graft copolymer (B-3) was 93%.

Reference Example 14: Graft copolymer (B-
4) In the example described in Production Reference Example 13 except that the composite rubber (S-3) was used as it was, polymerization and coagulation recovery were performed in the same manner except that acrylonitrile and styrene were all used as methyl methacrylate for the graft polymerization. A graft copolymer (B-4) was obtained. Further, the graft copolymer (B-
The acetone insoluble matter in 4) was 83%.

Reference Example 15: Graft copolymer (B-
Production of 5) By a known emulsion polymerization method, 50 parts of polybutadiene rubber having a mass average particle diameter of 0.3 μm was added to 1 part of acrylonitrile.
Diene rubber graft copolymer (B-5) obtained by graft-polymerizing a monomer mixture consisting of 5 parts and 35 parts of styrene.
Got

Reference Example 16: Graft copolymer (B-
Production of 6) By a known emulsion polymerization method, 50 parts of a polybutadiene rubber having a mass average particle diameter of 0.2 μm was mixed with a monomer mixture of 35 parts of methyl methacrylate, 12.5 parts of styrene and 2.5 parts of acrylonitrile. Graft-polymerized diene rubber-based graft copolymer (B-5) was obtained.

Reference Example 17: 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 1-8, Comparative Examples 1-7: Reference Examples 1-
Maleimide copolymers (A-1) to (A-
8), the graft copolymer obtained in Reference Examples 11 to 16 (B-
1) to (B-6) and, if necessary, the total amount of other copolymers (C-1) obtained in Reference Example 17 as shown in Table 2 is 10
After blending in an amount of 0 parts and 0.4 parts of ethylenebisstearylamide and 0.4 parts of barium stearate with a Henschel mixer, these were twin-screw extruder (manufactured by Japan Steel Works Ltd.). Manufactured, TEX-30α), 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.

[0054]

[Table 2]

The thermoplastic resin compositions of the present invention of Examples 1 to 8 have a high Izod impact strength and a high part cut softening point temperature, a good gloss and color appearance, and a good weatherability upon accelerated exposure. Was also excellent. On the other hand, Comparative Examples 1 to
The thermoplastic resin composition of No. 7 was inferior in any item of Izod impact strength, heat resistance, molding appearance, and weather resistance. Further, from Examples 1 and 3, when the maleimide-based monomer used in the maleimide-based copolymer was N-phenylmaleimide, the balance between Izod impact strength and Vicat softening point temperature was excellent. Further, according to Examples 1 and 6 to 7, when the particle diameter of the composite rubber used for the graft copolymer was in the range of 0.03 to 0.15 μm, the L * value was low and the coloring property was excellent. In particular, the thermoplastic resin compositions of Examples 1, 2, 4, and 5 can express a balance of high level Izod impact strength, heat resistance, molding appearance, and weather resistance which have hitherto been unknown.

[0056]

As described in detail above, according to the present invention, a good molding resin appearance and high heat resistance can be obtained, and further, a high level of mechanical strength such as impact resistance and weather resistance can be obtained. A thermoplastic resin composition having the same can be provided. In particular, the balance of impact resistance, heat 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 is used in various industries. It has a very high utility value as a material.

[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. In a triangular coordinate composed of an N-substituted maleimide unit, an alkyl (meth) acrylate unit, and another copolymerizable monomer, a point (1% by mass of N-substituted maleimide unit, alkyl ( (Meth) acrylate unit 4
5% by mass, other copolymerizable monomer 54% by mass), point b (N-substituted maleimide unit 1% by mass, alkyl (meth))
Acrylate unit 99% by mass, other copolymerizable monomer 0% by mass), and point c (N-substituted maleimide unit 55% by mass, alkyl (meth) acrylate unit 45% by mass,
Maleimide copolymer (A) having a monomer unit composition and a polyorganosiloxane / alkyl (meth) acrylate in a region formed by connecting 3 points of other copolymerizable monomers (0% by mass) A thermoplastic resin composition containing a graft copolymer (B) obtained by graft-polymerizing one or more vinyl-based monomers to a composite rubber (S). 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.