JP2003119332A - Styrene-based composite material and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a styrene-based composite material excellent in rigidity in which a layered compound is uniformly dispersed and to provide a method for producing the composite material. SOLUTION: This styrene-based composite material comprises (A) a resin composition composed of (A-1) an atactic polystyrene having one or more kinds of structural units represented by the general formula (1) [wherein R<1> may be same or different and represents at least one among hydrogen atom, a halogen atom, a 1-4C hydrocarbon group or oxygen atom, nitrogen atom and silicon atom; m is an integer of 0-5] or the atactic polystyrene and rubber-like elastomer and (A-2) a syndiotactic polystyrene having one or more kinds of structural units represented by the general formula (1) and (B) 0.1-30 wt.% layered compound which is released and dispersed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a styrene composite material having excellent rigidity and having a layered compound uniformly dispersed therein, and a method for producing the same.

[0002]

2. Description of the Related Art Styrene resin (syndiotactic polystyrene), which is an engineering plastic, has excellent physical properties, heat resistance, and moldability, and is a plastic material used in a wide range of fields such as home appliances and office automation equipment. Is useful as But in addition,
Materials having excellent physical properties are required.

On the other hand, in recent years, styrene resins such as syndiotactic polystyrene and atactic polystyrene, or syndiotactic polystyrene, atactic polystyrene and a rubber-like elastic body (eg HIPS (high impact polystyrene)) have been developed, It has been found that the solvent resistance is improved as compared with atactic polystyrene or a styrene-based resin composed of atactic polystyrene and a rubber-like elastic body (JP-A-11-2793).
47, 279348, 279349).

As a method for producing a composite resin material, many methods have been reported in which a layered silicate and an interlayer expander are kneaded with a polyolefin synthetic resin such as polypropylene. For example, JP-A-10-182892 discloses a clay composite material composed of thermoplastic resin / (organized) clay / modified resin. Japanese Patent Laid-Open No. 2000-178392
In the publication, a composition composed of an amorphous polystyrene and a layered compound is proposed. However, a reported example of a composition composed of a crystalline polystyrene-based synthetic resin such as syndiotactic polystyrene and a layered compound is as follows. Only.
That is, Macromolecules (Macromolucu)
les), Vol. 34, No. 9, pp. 2992-2999 (2001), syndiotactic polystyrene and a layered compound were dissolved and mixed in dichlorobenzene, and the crystallinity was determined by IR measurement of the obtained sample. It has been reported that the height is high and the α crystal disappears (no change in physical properties). However, there is no description about production by melt-kneading or a molding method.
In addition, there is no report on the composition comprising syndiotactic polystyrene and atactic polystyrene, or syndiotactic polystyrene and atactic polystyrene, a styrene resin composed of a rubber-like elastic material, and a layered compound.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a styrene-based composite material having excellent rigidity and in which a layered compound is uniformly dispersed, and a method for producing the same.

As a result of intensive studies to achieve the above object, the present inventors have found that a specific resin composition containing syndiotactic polystyrene and a styrene-based composite material containing a specific layered compound have excellent physical properties. The present invention has been completed and the present invention has been completed.

[0007]

According to the present invention, (A)
A styrene-based composite material containing a resin composition comprising the following components (A-1) and (A-2) and (B) a layered compound, in which the layered compound (B) is peeled and dispersed. (A-1) An atactic polystyrene having one or more structural units represented by the following general formula (1), or the atactic polystyrene and a rubber-like elastic body (A-2) represented by the following general formula (1) Syndiotactic polystyrene having at least one structural unit

[0008]

[Chemical 3]

[In the formula, R ^1's may be the same or different and each contains at least one of a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or an oxygen atom, a nitrogen atom and a silicon atom. Shows a substituent, m shows the integer of 0-5. ]

Preferably, the resin composition (A) contains 30 to 95% by weight of the component (A-1) and 70 of the component (A-2).
Resin composition (A) of 99.9 to 70
A styrene-based composite material containing 0.1% to 30% by weight of the layered compound (B).

Further, preferably, the main skeleton (C) has at least one structural unit represented by the above general formula (1) or the following general formula (2) and is modified with one or more functional groups. It is a styrene-based composite material containing a functional group-modified organic (co) polymer.

[0012]

[Chemical 4]

[In the formula, R ^{2 s} may be the same or different and each represents a hydrocarbon group having 1 to 4 carbon atoms or a substituent containing at least one of oxygen atom, nitrogen atom and silicon atom. ]

Preferably, the resin composition (A) 50-9
9.45% by weight, layered compound (B) 0.05 to 30% by weight, and functional group-modified organic (co) polymer (C) 0.5 to 2
It is a styrene-based composite material containing 0% by weight.

Preferably, the functional group-modified organic (co) polymer (C) has, as a main skeleton, only the structural unit represented by the general formula (2), and R ² is a methyl group or an oxygen atom. ,
A substituent containing at least one of a nitrogen atom and a silicon atom. Preferably, the melting point of syndiotactic polystyrene (A-2) is 255 ° C. or lower. Preferably,
The layered compound (B) is a clay, a clay mineral, or an ion-exchangeable layered compound. Preferably, the layered compound (B) is
It is an organically modified layered compound obtained by exchanging exchangeable cations existing between layers with organic onium ions.

Further, according to the present invention, the resin composition (A)
And the layered compound (B), or the resin composition (A), the layered compound (B) and the functional group-modified organic (co) polymer (C)
A method for producing the above-mentioned styrene-based composite material by melt-kneading is provided.

Preferably, the syndiotactic polystyrene (A-2) is melt-kneaded at a melting point or higher and 270 ° C. or lower. Preferably, the exchangeable cations existing between the layers of the layered compound (B) are exchanged with organic onium ions.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. 1. Resin composition (A) (1) Atactic polystyrene, or atactic polystyrene and rubber-like elastic body (A-1) Atactic polystyrene has one or more structural units represented by the following general formula (1).

[0019]

[Chemical 5]

[In the formula, R ^{1 s} may be the same or different and each contains at least one of a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or an oxygen atom, a nitrogen atom and a silicon atom. Shows a substituent, m shows the integer of 0-5. ]

Specific examples of R ¹ include hydrogen, a chloro group,
Examples thereof include a bromine group, a methyl group, an ethyl group, and a tert-butyl group. Of these, hydrogen, bromine group and methyl group are preferable. Examples of the substituent containing at least one kind of oxygen atom, nitrogen atom and silicon atom include alkoxy groups such as methoxy group, ethoxy group and propoxy group, dimethylamino group, diethylamino group, methylethylamino group, dipropyl group. Examples thereof include dialkylamino groups such as amino groups and trialkoxysilyl groups such as trimethoxysilyl group and triethoxysilyl group. Of these, a dimethylamino group, a diethylamino group, a trimethoxysilyl group, and a triethoxysilyl group are preferable. Specific examples of the monomer giving the above structural unit include styrene, p-methylstyrene, p-ethylstyrene, p-tert-butylstyrene, p-chlorostyrene, p-bromostyrene and the like.

The molecular weight of atactic polystyrene is not particularly limited, but the weight average molecular weight thereof is generally 10,000 or more, preferably 50,000 or more. Here, if the weight average molecular weight is less than 10,000, the thermal properties and mechanical properties of the obtained molded article are deteriorated, which is not preferable. Furthermore, the molecular weight distribution is not limited to a wide or narrow range, and various kinds can be applied.

The atactic polystyrene of the present invention is, for example, polystyrene, poly (alkylstyrene), poly (halogenated styrene), poly (halogenated alkylstyrene), poly (alkoxystyrene), or a copolymer containing these as main components. It is a polymer. In the case of a copolymer, other copolymer components include acrylonitrile, vinyl cyan compounds such as methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate,
Acrylic esters such as butyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, 2 -Methacrylic acid esters such as ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate, maleimide, N-methylmaleimide, N-ethylmaleimide, N
-Butyl maleimide, N-cyclohexyl maleimide,
N-phenylmaleimide, N- (p-bromophenyl)
Other examples include maleimide compounds such as maleimide, ethylene, propylene, butadiene, and isoprene.

Atactic polystyrene is solution polymerized,
It can be produced by a known polymerization method such as bulk polymerization, suspension polymerization, and bulk-suspension polymerization.

In order to improve impact resistance, (A
A rubber-like elastic body may be used in combination as a part of the component (-1) depending on the purpose. Specific examples of the rubber-like elastic body include
For example, natural rubber, polybutadiene, polyisoprene,
Polyisobutylene, neoprene, polysulfide rubber,
Thiocol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, styrene-butadiene block copolymer (SBR), hydrogenated styrene-
Butadiene block copolymer (SEB, SEBC), styrene-butadiene-styrene block copolymer (SB
S), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-
Styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEP)
S), or ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM), or butadiene-acrylonitrile-styrene-core shell rubber (ABS), methyl methacrylate-butadiene-styrene-core shell rubber (MBS), methyl methacrylate-butyl acrylate. -Styrene-core shell rubber (MAS), octyl acrylate-butadiene-styrene-core shell rubber (MABS), alkyl acrylate-butadiene-acrylonitrile-styrene-core shell rubber (AABS), butadiene-styrene-core shell rubber (SBR), methyl methacrylate- Core-shell type elastic particles such as butyl-acrylate-siloxane and other siloxane-containing core-shell rubbers, or modified Rubber, and the like. Among them, especially SBR, SEB, SBS, SEBS, SI
R, SEP, SIS, SEPS, core shell rubber, EP
M, EPDM, or rubber modified with these is preferably used. These rubber-like elastic bodies may be used alone or in combination.
It is possible to mix and use one or more species.

When atactic polystyrene and a rubber-like elastic material are used in combination, the compounding ratio of the rubber-like elastic material is as follows:
It is 80% by weight or less, preferably 60% by weight or less, and more preferably 50% by weight or less in the component (A-1). 8
If it exceeds 0% by weight, solvent resistance and elastic modulus may decrease.

(2) Syndiotactic Polystyrene (A-2) The syndiotactic polystyrene (A-2) has at least one structural unit represented by the above general formula (1). Specific examples of R ^{1 in the} general formula (1) and the monomer are the same as in the case of atactic polystyrene.

The molecular weight of the syndiotactic polystyrene is not particularly limited, but the weight average molecular weight is preferably 10,000 or more, more preferably 50,000 or more. Further, the molecular weight distribution is not limited in width and width, and various kinds can be applied.

The syndiotactic structure means that the steric structure is a syndiotactic structure, that is, side chains of phenyl groups and substituted phenyl groups are alternately opposite to the main chain formed from carbon-carbon bonds. The tacticity is determined by nuclear magnetic resonance ( ¹³ C-NMR method) using isotope carbon.
^The tacticity measured by ¹³ C-NMR can be indicated by the abundance ratio of a plurality of continuous constitutional units, for example, diad in the case of 2, triad in the case of 3, and pentad in the case of 5. .

The syndiotactic polystyrene of the present invention is usually a racemic dyad having a syndiotacticity of 75% or more, preferably 85% or more, or a racemic pentad having a syndiotacticity of 30% or more, preferably 50% or more. Polystyrene, poly (alkylstyrene), poly (halogenated styrene), poly (halogenated alkylstyrene), and poly (alkoxystyrene).

The melting point of syndiotactic polystyrene, which is generally composed only of unsubstituted styrene, is about 270.
℃. The syndiotactic polystyrene used in the styrene-based composite material this time preferably has a melting point of 255.
It is below ℃. As an example of syndiotactic polystyrene, p-methylstyrene copolymerized syndiotactic polystyrene composed of p-methylstyrene having a melting point of about 230 ° C. and unsubstituted styrene (manufactured by Idemitsu Petrochemical Co .; E
101A12) and the like.

As a method for producing syndiotactic polystyrene, a known method may be used.
A method of polymerizing a styrene-based monomer using a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst in an inert hydrocarbon solvent or in the absence of a solvent is disclosed (JP-A-62-187709). etc).

(3) The compounded resin composition (A) contains the above component (A-1), preferably 30 to 95% by weight, more preferably 50 to 90% by weight, and the above component (A-2). It is preferably 70 to 5% by weight, more preferably 50 to 10% by weight. If the ratio of the component (A-1) is less than 30% by weight, the properties of atactic polystyrene may be lost and the impact resistance may decrease, and if it exceeds 95% by weight, the effect of solvent resistance cannot be exhibited. There is.

2. Layered Compound (B) Since the layered compound (B) needs to be peeled and dispersed in the resin composition (A), it is preferably swellable and is preferably a silicate. In the present invention, examples of the layered compound (B) include clay, clay minerals and ion-exchangeable layered compounds. Clay is an aggregate of fine hydrated silicate minerals, which is a substance that produces plasticity when kneaded with an appropriate amount of water, exhibits rigidity when dried, and sinters when baked at high temperatures. Further, the clay mineral refers to a hydrous silicate that is a main component of clay. These are not limited to naturally occurring ones, but may be artificially synthesized ones. The ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds or the like are stacked in parallel with each other with weak binding forces, and the ions contained therein are exchangeable. Some clay minerals are ion-exchangeable layered compounds.

Examples of clay minerals include phyllosilicates. Examples of the phyllosilicates include phyllosilicate and phyllosilicate. As a phyllosilicate, as a natural product, montmorillonite belonging to the smectite group,
Saponite, hectorite, illite belonging to the mica family,
Examples thereof include mixed layer minerals of sericite and smectite group and mica group or mica group and vermiculite group. In addition, as synthetic products, tetrafluorosilicon mica, laponite, smecton and the like can be mentioned. In addition, α-Zr (HP
O ₄ ) ₂ , γ-Zr (HPO ₄ ) ₂ , α-Ti (HPO ₄ ).
₂ and γ-Ti (HPO ₄ ) _{2 and} other ionic crystalline compounds having a layered crystal structure that is not a clay mineral.

In the present invention, the layer charge is 0.05 to 0.
It is preferable to use a 2: 1 type layered compound having 8, especially 0.1 to 0.7, and among them, smectites (layer charge: 0.2 to 0.6) and swelling synthetic mica are more preferable.
As smectites, hectorite, saponite,
Montmorillonite is preferable, and montmorillonite is particularly preferable. Further, as the swelling synthetic mica, fluorine tetrasilicon mica (layer charge 0.6) is preferable.

The shape of the clay, clay mineral or ion-exchangeable layered compound used in the present invention is preferably particles having a volume average particle diameter of 10 μm or less, and more preferably particles having a volume average particle diameter of 3 μm or less. Generally, the particle shape of the particles has a particle size distribution, but the volume average particle diameter is 10 μm or less and the volume average particle diameter is 3.0 μm.
It is preferable that the following content ratio has a particle size distribution of 10% by mass or more, the volume average particle size is 10 μm or less, and the volume ratio of the volume average particle size is 1.5 μm or less is 1
It is further preferable to have a particle size distribution that is 0 mass% or more. As a method for measuring the volume average particle diameter and the content ratio, for example, a device for measuring the particle diameter by light transmittance with a laser beam (GALAI Production Ltd.
Manufactured by CIS-1).

The layer structure of the layered compound (B) is preferably 5 to 100 layers, and more preferably 5 to 50 layers. Here, the level of the predetermined number of layers means that about 90% or more of the layered compound (B) is peeled to a predetermined level. In the layered compound (B),
By adjusting the target resin by applying a shear stress, the resin can be peeled and dispersed to a desired layer level.

The layered compound (B) is preferably an organized layered compound obtained by exchanging exchangeable cations existing between layers with an organic onium ion which is an interlayer expanding agent. The organic onium ion used in the present invention is preferably an alkyl onium ion, and has an alkyl group having 1 to 32 carbon atoms, preferably 1 to 18 carbon atoms, a phosphonium ion, a sulfonium ion, and an onium derived from a heteroaromatic ring. It is represented by Aeon. By allowing an onium ion structure to exist between the layers of the layered compound (B), a hydrocarbon structure having a small intermolecular force can be introduced between the layers of the negatively charged silicate layer. The type of the organic onium ion is not particularly limited, but an ammonium ion, a phosphonium ion, and an onium ion derived from a heteroaromatic ring are preferable from the viewpoint of easy availability and stability.

Examples of ammonium ions include primary ammonium such as dodecyl ammonium, hexadecyl ammonium and octadecyl ammonium, secondary ammonium such as methyl dodecyl ammonium, butyl dodecyl ammonium and methyl octadecyl ammonium, dimethyl dodecyl ammonium, dimethyl hexadecyl ammonium. , Tertiary ammonium such as dimethyl octadecyl ammonium, diphenyl dodecyl ammonium and diphenyl octadecyl ammonium, quaternary ammonium having the same alkyl group such as tetraethyl ammonium, tetrabutyl ammonium and tetraoctyl ammonium, trimethyl octyl ammonium, trimethyl decyl ammonium, trimethyl Dodecyl ammonium, trimethyl tet Decyl ammonium, trimethyl hexadecyl ammonium, trimethyl octadecyl ammonium, trimethyl eicosanyl ammonium, trimethyl octadecenyl ammonium, trimethyl octadecadienyl ammonium and other trimethyl alkyl ammonium, triethyl dodecyl ammonium, triethyl tetradecyl ammonium, triethyl hexadecyl ammonium , Triethyl alkyl ammonium such as triethyl octadecyl ammonium, tributyl dodecyl ammonium, tributyl tetradecyl ammonium, tributyl hexadecyl ammonium, tributyl alkyl ammonium such as tributyl octadecyl ammonium, dimethyl dioctyl ammonium, dimethyl didecyl ammonium, dimethyl dite Dimethyldialkylammonium such as radecylammonium, dimethyldihexadecylammonium, dimethyldioctadecylammonium, dimethyldioctadecenylammonium, dimethyldioctadecadienylammonium, diethyldidodecylammonium, diethylditetradecylammonium, diethyldihexa Decylammonium, diethyldialkylammonium such as diethyldioctadecylammonium, dibutyldidodecylammonium,
Dibutylditetradecylammonium, dibutyldihexadecylammonium, dibutyldioctadecylammonium, etc. dibutyldialkylammonium, methylbenzyldihexadecylammonium, etc., methylbenzyldialkylammonium, dibenzyldihexadecylammonium, etc., dibenzyldialkylammonium, trioctyl Trialkylmethylammonium such as methylammonium, tridodecylmethylammonium and tritetradecylmethylammonium, trialkylethylammonium such as trioctylethylammonium and tridodecylethylammonium, trialkylbutyl such as trioctylbutylammonium and tridodecylbutylammonium Aroma such as ammonium and trimethylbenzylammonium Quaternary ammonium having, and ion of the quaternary ammonium ions derived from an aromatic amine such as trimethylphenyl ammonium.

Examples of the phosphonium ion include tetrabutylphosphonium, tetraoctylphosphonium, trimethyldecylphosphonium, trimethyldodecylphosphonium, trimethylhexadecylphosphonium, trimethyloctadecylphosphonium, tributyldodecylphosphonium, tributylhexadecylphosphonium and tributyloctadecylphosphonium. Examples include phosphonium ions.

Examples of the onium ion derived from the heteroaromatic ring include ions such as pyridinium and quinolinium.

Of these, octadecyl ammonium, dimethyldioctadecyl ammonium, and tributylhexylphosphonium are preferable.

As the organically modified layered compound, those produced by themselves and commercially available products can be used. As an example of self-manufacturing, a swellable synthetic mica is added to pure water to prepare a slurry, an organic onium agent is added thereto, and the mixture is stirred.
A method of obtaining an organically modified layered compound by centrifuging, drying and pulverizing may be mentioned. An example of a commercially available product is Cloisite 20A which is an organized montmorillonite.

The layered compound (B) may be coupled with a reactive functional group-containing coupling agent. Coupling with such a coupling agent may provide better mechanical strength and heat resistance.

As the coupling agent, isocyanate is used.
Compounds, organosilane compounds, organic titanate compounds
Compounds, organic borane compounds, epoxy compounds, etc.
It In addition, as a reactive functional group possessed by these compounds
Are, for example, epoxy group, mercapto group, ureido group,
Isocyanato group, amino group, hydroxyl group, vinyl group
Be done.

Of these coupling agents, organosilane compounds are particularly preferable, and specific examples thereof include γ-glycidoxypropyltrimethoxysilane and γ.
-Glycidoxypropyltriethoxysilane, β-
Epoxy group-containing alkoxysilane compounds such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane,
γ-Mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane and other mercapto group-containing alkoxysilane compounds, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ- (2-ureidoethyl) aminopropyl Ureido group-containing alkoxysilane compounds such as trimethoxysilane, γ-isocyanatopropyltrimethoxysilane,
γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanate Isocyanato group-containing alkoxysilane compounds such as natopropyltrichlorosilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, etc. Amino group-containing alkoxysilane compounds, γ-hydroxypropyltrimethoxysilane, γ-hydroxypropyltriethoxysilane and other hydroxyl group-containing alkoxysilane compounds, γ-methacryloxypropyltrimethoxy Silane, vinyltrimethoxysilane, N-β- (N- vinylbenzylaminoethyl)-.gamma.-aminopropyltrimethoxysilane hydrochloride vinyl group-containing alkoxysilane compounds such like. Of these, γ-methacryloxyproproxytrimethoxysilane (3-methacryloxyproproxytrimethoxysilane) and γ-aminoproproxytrimethoxysilane (3-aminoproproxytrimethoxysilane) are preferable.

The method of coupling the layered compound (B) with the reactive functional group-containing coupling agent is not particularly limited, and examples thereof include a method of adsorbing the coupling agent to the layered compound in a polar solvent, and a coupling agent during kneading. How to add,
Examples thereof include a method of directly adsorbing the coupling agent to the layered compound in a mortar or the like.

In the styrenic composite material of the present invention, the resin composition (A) is preferably 99.9 to 70% by weight,
More preferably, it is contained in an amount of 99.9 to 80% by weight, and the layered compound (B) is contained in an amount of preferably 0.1 to 30% by weight, more preferably 0.1 to 20% by weight.

3. Functional group-modified organic (co) polymer (C) The functional group-modified organic (co) polymer (C) is modified with one or more functional groups, and the main skeleton is represented by the following general formula (1), or , Having at least one structural unit represented by the following general formula (2). The functional group-modified organic (co) polymer (C) has 1 or 2 structural units represented by the general formula (1).
One or more kinds of the structural unit represented by the general formula (2), or two or more kinds of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2). You may.

[0051]

[Chemical 6]

[In the formula, R ^{1 s} may be the same or different and each contains at least one of a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or an oxygen atom, a nitrogen atom and a silicon atom. Shows a substituent, m shows the integer of 0-5. ]

Specific examples of R ^{1 in the} general formula (1) and the monomer are the same as in the case of atactic polystyrene.

[0054]

[Chemical 7]

[In the formula, R ^{2 s} may be the same or different and each represents a hydrocarbon group having 1 to 4 carbon atoms or a substituent containing at least one of an oxygen atom, a nitrogen atom and a silicon atom. ]

Specific examples of R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group,
Examples thereof include isobutyl group and tert-butyl group. A methyl group is preferred. Examples of the substituent containing at least one kind of oxygen atom, nitrogen atom and silicon atom include alkoxy groups such as methoxy group, ethoxy group and propoxy group, dimethylamino group, diethylamino group, methylethylamino group, dipropyl group. Examples thereof include dialkylamino groups such as amino groups and trialkoxysilyl groups such as trimethoxysilyl group and triethoxysilyl group. Of these, a dimethylamino group, a diethylamino group, a trimethoxysilyl group, and a triethoxysilyl group are preferable.

Specific examples of the functional group contained in the functional group-modified organic (co) polymer (C) include a hydroxyl group, a carboxyl group (fumaric acid), a dicarboxylic acid anhydride group (maleic anhydride, itaconic anhydride, Phthalic anhydride), epoxy group, amino group, amide group, oxazoline group and the like. Of these, a carboxyl group and a dicarboxylic acid anhydride group are preferred.

Among the functional group-modified organic (co) polymers (C), those having at least one structural unit represented by the above general formula (1) include, for example, maleic acid-modified atactic polystyrene resin and anhydrous. Examples thereof include maleic acid-modified atactic polystyrene resin, maleimide acid-modified atactic polystyrene resin, epoxy group-containing compound-modified atactic polystyrene resin, and acid-modified styrene-based thermoplastic elastomer (eg, maleic acid-modified SEBS).

Further, a functional group-modified organic (co) polymer (C)
Among them, those having at least one structural unit represented by the general formula (2) include maleic acid-modified aromatic polyether resins, maleic anhydride-modified aromatic polyether resins, and fumaric acid-modified aromatic polyethers. Examples thereof include resins and epoxy group-containing compound-modified aromatic polyether resins.

The amount of modification in the functional group-modified organic (co) polymer (C) is based on 100 parts by weight of the organic (co) polymer having the structural unit represented by the general formula (1) or (2).
0.1 to 5.0 parts by weight, more preferably 0.5 to 4.
It is selected in the range of 0 parts by weight. If the addition amount is less than 0.1 parts by weight, the modification ratio is low, and the obtained modified product may be substantially the same as the unmodified product, and even if it is added in excess of 5.0 parts by weight. The effect of improving the modification rate is small.

When the styrenic composite material of the present invention contains a functional group-modified organic (co) polymer (C), the resin composition (A) is preferably 50 to 99.45% by weight,
More preferably 60 to 99.4% by weight, the layered compound (B) is preferably 0.05 to 30% by weight, more preferably 0.1 to 20% by weight, the functional group-modified organic (co) polymer (C ) Is preferably contained in an amount of 0.5 to 20% by weight.

4. Method for producing styrene-based composite material The styrene-based composite material of the present invention is the above resin composition (A).
And the layered compound (B), or the resin composition (A), the layered compound (B) and the functional group-modified organic (co) polymer (C)
Can be produced by melt-kneading. Kneading refers to an operation of applying a shearing force to the blended components. For the operation, a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer, a roll, a plastomill or the like can be used. The rotation speed of the stirring blade is usually 1 to 3,000 rp
m, preferably 10 to 1,000 rpm.
The kneading pressure is 0 to 40 MPa, preferably 0.1.
It is -10 MPa. The kneading temperature is preferably not lower than the melting point of the syndiotactic polystyrene (A-2) and not higher than 270 ° C, more preferably 240 to 260 ° C. The kneading treatment time may be 30 seconds to 1 hour. The kneading treatment is preferably performed in an inert gas atmosphere. Depending on the case, an operation of adding steam or removing a volatile component in the styrene-based composite material under reduced pressure may be performed.

The styrenic composite material of the present invention is a resin composition (A) and a layered compound (B), or a resin composition (A), a layered compound (B) and a functional group-modified organic (co).
The polymer (C) may be melt-kneaded at the same time, or the layered compound (B) and the functional group-modified organic (co) polymer (C) may be previously melt-kneaded to contain the layered compound in the functional group-modified organic compound. The resin composition (A) may be melt-kneaded to produce a (co) polymer. When the layered compound (B) and the functional group-modified organic (co) polymer (C) are melt-kneaded in advance, the layered compound (B) in the styrene-based composite material is improved in peeling / dispersing property and the physical property improving effect is improved. I have something to do.

In the method for producing a styrenic composite material of the present invention, it is preferable that the layered compound (B) is previously exchanged for the cation existing between the layers with the above organic onium ion by the above method. The layered compound (B) is
You may treat with the said reactive functional group containing silane compound by the above method. At this time, when these two processes are performed together, the order is not particularly limited.

5. Styrene-based composite material The styrene-based composite material obtained by the present invention has excellent rigidity and the layered compound is uniformly dispersed.

The styrenic composite material of the present invention generally comprises
Molding pressure 2 to 40 MPa, molding temperature 250 to 320 ° C.,
It can be preferably molded at 260 to 300 ° C.
For example, injection molding is preferable, and as a molding machine, an extrusion molding machine, an injection molding machine, or the like can be used, and the shearing treatment and the molding can be simultaneously performed.

The styrenic composite material of the present invention can be used for various purposes and is not particularly limited. Examples of applications for automotive parts include radiator grilles, grilles, marks, back panels, door mirrors, wheel caps, air spoilers, and motorcycle cowls as exterior parts, and instrument panels, meter hoods, pillars as interior parts. Examples include glove boxes, console boxes, speaker boxes, lids, and the like.
For electrical appliances, housings for AV equipment,
Examples include chassis, cassette cases, CD magazines, remote control cases, etc., for electric refrigerators, linings, trays, arms, door caps, handles, etc., and for vacuum cleaners, housings, handles, pipes, suction ports, etc. For air conditioners, there are housings, fans, remote control cases, etc.
Examples include washing machines, parts for lighting equipment, and battery cases. Examples of general-purpose applications include housings, chassis, ribbon cassettes and trays for printers and copiers, and housings, floppy disk shells, keyboards and the like for personal computers. Further, a telephone, a housing for communication equipment, a handset, a mechanical chassis and the like can be mentioned. For other equipment, sewing machines, registers, typewriters, calculators, optical equipment,
Examples include musical instruments. Furthermore, miscellaneous goods and remote control cars,
It is also used for toys such as blocks, pachinko machine parts, surfboards, helmets, leisure and sports equipment. Toilet bowls, toilet lids, tanks, shower hygiene items, lunch boxes, various containers, household items such as pots, building materials, housing parts, furniture,
Also used for stationery. As an application for industrial structural materials,
Pipe, container, tray, uniaxial by extrusion and drawing,
It is also suitably used for applications such as biaxially stretched films, sheets, and fibrous molded articles by spinning.

[0068]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. Various measuring methods in Examples and Comparative Examples are as follows.

(1) Measurement of Filler Dispersion State As a test piece, an ultrathin section of a styrene-based composite material having a thickness of 130 nm was used. Transmission electron microscope (made by JEOL Ltd.,
Product name: JEM-1010), acceleration voltage 100
The dispersed state of the filler was observed and photographed at a magnification of 40,000 to 1,000,000 times at kV. Select a region where 100 or more dispersed particles exist, and manually measure the layer thickness using a graduated ruler, or if necessary, NIH Image from the National Institutes of Health.
e V. It was measured by processing with 1.57.

(2) Storage elastic modulus Sheets (width 4 cm ×) by hot pressing at a molding temperature of 250 ° C.
4 cm in length × 300 μm in thickness) was prepared and used as a sample for measuring storage elastic modulus. As the measuring device, a fully automatic solid viscoelasticity measuring device (manufactured by Iwamoto Seisakusho Co., Ltd., trade name: viscoelasticity spectrometer typeVES-F-III) was used. Measurement conditions are initial load 0.5N, frequency 10H
z, the starting temperature was 0 ° C, and the ending temperature was 250 ° C.

(3) Flexural Modulus Using the obtained pellets, injection molding was carried out at a resin temperature of 260 ° C. and a mold temperature of 80 ° C. to obtain bending test pieces. The flexural modulus of the obtained test piece was measured according to JIS-K-7203.

(4) Tensile elastic modulus Using the pellets thus obtained, injection molding was carried out at a resin temperature of 260 ° C. and a mold temperature of 80 ° C. to obtain tensile test pieces. The flexural modulus of the obtained test piece was measured according to JIS-K-7113.

Example 1 <Resin composition (A) / organized layered compound (B)> As the resin composition, an alloy having the following components was used. High-impact polystyrene (HIPS) 80 wt% (Idemitsu Petrochemical, trade name: HT52) Syndiotactic polystyrene (SPS) 20 wt% (Idemitsu Petrochemical, trade name: 201AE) Styrene-p-methylstyrene copolymer (P-Methylstyrene content: 14 mol%) Weight average molecular weight (Mw) = 17.5 × 10 ⁴ Mw / Mn = 2.0 Melting point 238 ° C.

19,000 g (95% by weight) of the above resin composition and organic montmorillonite (Southern)
Made by Clay Products, trade name: Clois
ite20A) 1,000 g (5% by weight) of a twin-screw extruder with a vent (manufactured by Toshiba Machine Co., Ltd., trade name: TEM-35)
, 260 ° C, rotation speed 400 rpm, discharge rate 2
Melt kneading was carried out under the condition of 0 kg / h. The resin composition in a molten state was immediately introduced into water as a strand and pelletized with a take-off machine equipped with a cutter. This pellet at 80 ℃
After drying for 12 hours, the mixture was injection-molded and the filler dispersion state and physical properties were measured. As a result, regarding the filler dispersion state, it was confirmed that the peeling proceeded to the level of 10 to 15 layers, and the filler was uniformly dispersed in the resin composition of the matrix. The results of each physical property are shown in Table 1.

Example 2 <Resin composition (A) / organized layered compound (B) / functional group-modified organic polymer (C)> In Example 1, 18,620 g (93.1% by weight) of the resin composition was added. ), 1,000 g (5% by weight) of organized montmorillonite, and 380 g (1.9 g of fumaric acid-modified polyphenylene ether).
% By weight) (synthesized with reference to JP-A-8-31196, modification rate 0.5% by weight, polystyrene-equivalent molecular weight: M
(n = 13000, R ^{2 of the} general formula (2) is a methyl group)
Except that it was used, the same operation as in Example 1 was performed to measure the filler dispersion state and physical properties. As a result, regarding the filler dispersed state, it was confirmed that the peeling proceeded to the level of 5 to 10 layers, and the filler was uniformly dispersed in the resin composition of the matrix. The results of each physical property are shown in Table 1.

Comparative Example 1 <Resin Composition (A)> The same operation as in Example 1 was carried out except that the organized montmorillonite was not used, and the physical properties were measured. The results are shown in Table 1.

[0077]

[Table 1]

[0078]

According to the present invention, it is possible to provide a styrene-based composite material which is excellent in rigidity and in which a layered compound is uniformly dispersed, and a method for producing the same.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing a method for producing a styrene-based composite material of the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 71/12 C08L 71/12 (72) Inventor Yoshihiko Horio 1F Amezaki, Ichihara-shi, Chiba 1F term ( (Reference) 4F070 AA04 AA17 AA18 AA52 AB01 AB08 AB11 AB23 AC27 AD01 AE01 FA03 FA13 FA17 FB06 4J002 AC01Y AC03Y AC06Y AC08Y AC09Y BC09W BC03X BC BC03 BC08BC BC0807 BC08 BC08 BC08 BC08 BC08 BC08 BC10 BC08 BC08 BC08 BC08 BC10 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC10 BC08 BC08 BC08 BC08 BC10 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC10 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC10 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC10 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC10 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC08 BC10 BC08 BC08 BC08 BC08 BC07 BC08 BC12W BC12X BC124 BG04Y BN12Y BN14Y BN15Y BN16Y BP01Y CH04Y CH074 CK02Y CN02Y CP03Y CP17Y DH046 DJ006 DJ036 DJ056 FA016 FB086 FB106 FB126 FB136 FB146 FB156 FB266 GC00 GG01 GN00GM00G00

Claims (11)

[Claims] 1. (A) The following components (A-1) and (A-
A styrene-based composite material comprising a resin composition comprising 2) and (B) a layered compound, wherein the layered compound (B) is peeled and dispersed. (A-1) An atactic polystyrene having one or more structural units represented by the following general formula (1), or the atactic polystyrene and a rubber-like elastic body (A-2) represented by the following general formula (1) Syndiotactic polystyrene having at least one structural unit [In the formula, R ¹ may be the same or different, and a hydrogen atom,
A halogen atom, a hydrocarbon group having 1 to 4 carbon atoms or a substituent containing at least one of an oxygen atom, a nitrogen atom and a silicon atom is shown, and m is an integer of 0 to 5. ] 2. The resin composition (A) is the same as the component (A).
-1) 30 to 95% by weight, and the component (A-2) 70
The styrene-based composite material according to claim 1, wherein the resin composition (A) is 99.9 to 70% by weight, and the layered compound (B) is 0.1 to 30% by weight. 3. A structural unit represented by the general formula (1) or the following general formula (2) is used as the main skeleton (C).
The styrene-based composite material according to claim 1 or 2, which has one or more kinds and contains a functional group-modified organic (co) polymer modified with one or more kinds of functional groups. [Chemical 2] [In the formula, R ^{2 s} may be the same or different and have 1 to 1 carbon atoms.
4 represents a hydrocarbon group or a substituent containing at least one of an oxygen atom, a nitrogen atom and a silicon atom. ] 4. The resin composition (A) 50 to 99.45.
% By weight, 0.05 to 30% by weight of the layer compound (B),
And the functional group-modified organic (co) polymer (C) 0.5 to 2
The styrenic composite material according to claim 3, containing 0% by weight. 5. The functional group-modified organic (co) polymer (C)
Is a substituent having only the structural unit represented by the general formula (2) as a main skeleton, and R ² is a methyl group or a substituent containing any one or more of an oxygen atom, a nitrogen atom and a silicon atom. Item 3. The styrene-based composite material according to Item 3 or 4. 6. The styrene-based composite material according to claim 1, wherein the syndiotactic polystyrene (A-2) has a melting point of 255 ° C. or lower. 7. The styrene-based composite material according to claim 1, wherein the layered compound (B) is clay, a clay mineral, or an ion-exchangeable layered compound. 8. The styrenic composite according to any one of claims 1 to 7, wherein the layered compound (B) is an organized layered compound obtained by exchanging exchangeable cations existing between layers with organic onium ions. material. 9. The resin composition (A) and the layered compound (B), or the resin composition (A), the layered compound (B) and the functional group-modified organic (co) polymer (C). )
The method for producing a styrene-based composite material according to claim 1, wherein the compound is melt-kneaded. 10. The method for producing a styrene-based composite material according to claim 9, wherein the syndiotactic polystyrene (A-2) is melt-kneaded at a melting point or higher and 270 ° C. or lower. 11. The method for producing a styrene-based composite material according to claim 9, wherein the exchangeable cations existing between the layers of the layered compound (B) are exchanged with organic onium ions.