JPH07331092A - Thermoplastic resin composition - Google Patents

Abstract

(57) [Summary] [Structure] Containing an interlayer compound having a cation-exchange layered silicate having a reactive functional group as a host and an organic onium ion as a guest, and a thermoplastic resin capable of reacting with the reactive functional group. Then, the interlayer compound is used as the inorganic ash content of 0.1 to 20.
A thermoplastic resin composition containing 1% by weight, and a thermoplastic resin composition containing an aromatic polycarbonate resin and a layered silicate, wherein the amount of inorganic ash in the thermoplastic resin composition is 0.25 to 10% by weight. A thermoplastic resin composition in which the product of the parallel transmittance P (%) of parallel visible light and the inorganic ash content A (% by weight) with respect to a molded product of a thermoplastic resin composition having a thickness of 3 mm satisfies the following formula a: . [Equation 1] P × A ≧ 20 (A) [Effect] Excellent strength and rigidity, toughness is not impaired, specific gravity does not increase, good molding surface properties, melt flowability, and low molding shrinkage. It has excellent moldability such as rate. Further, when a transparent thermoplastic resin typified by an aromatic polycarbonate resin is used as a matrix, it has excellent transparency.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition comprising a thermoplastic resin and a layered silicate or intercalation compound which is extremely uniformly dispersed in the thermoplastic resin matrix.

[0002]

2. Description of the Related Art Conventionally, various fillers have been used for the purpose of increasing strength and rigidity of thermoplastic resin materials and increasing dimensional accuracy.
For example, glass fibers, carbon fibers, inorganic fibers such as potassium titanate whiskers, and glass flakes, glass beads, talc, mica, kaolin, wollastonite, and other inorganic powders have been compounded. However, although these methods increase strength and rigidity, they have drawbacks of impairing toughness, increasing specific gravity, and decreasing surface appearance.
Such defects in the mixing of fillers are generally considered to be due to poor dispersion of fillers or an excessively large size of the dispersion, and poor adhesion at the interface with the matrix resin. Various attempts have been made such as surface treatment, pulverization, and devising the shape.

For example, in JP-A-61-266461, in an attempt to improve the adhesion at the interface, a polyphenylene sulfide resin is blended with a silicic acid and / or a silicate treated with a silane coupling agent to obtain an untreated product. Although it is described that the mechanical properties and the moisture resistance are improved as compared with, the dispersion size was relatively large and there was a problem in the molding surface property.

As an attempt to reduce the dispersion size, there has been proposed a method of dispersing an intercalation compound in which an organic onium ion is intercalated in a layered silicate having a cation exchange ability in a thermoplastic resin matrix,
For example, regarding polyamide resin, JP-A-48-103
Japanese Patent Application Laid-Open No. 3-153, No. 6599, Japanese Patent Application Laid-Open No. 51-109998, Japanese Patent Application Laid-Open No. 58-35542, Japanese Patent Application Laid-Open No. 62-74957, and Japanese Patent Application No. 5-245199 disclose the aromatic polyester resin. 62846 publication,
They are disclosed in Japanese Patent Application No. 5-245200. By these techniques, the layered silicate is extremely finely dispersed, and the strength and rigidity can be remarkably improved and good molding surface properties can be achieved with a small amount of addition, but retention of toughness is not always satisfactory. .

Further, in JP-A-4-80259 and JP-A-4-178459, a hindered phenol compound, a silane coupling agent and a hindered phenol compound are added to a system of a polyamide resin and a layered silicate uniformly dispersed therein. A resin composition for a stretched polyamide film, which is obtained by adding a titanate coupling agent or the like, is disclosed. However, the mixing method of these additives, mixing into a composition in which a layered silicate is uniformly dispersed in polyamide, simultaneous mixing at the time of dispersing the layered silicate in polyamide, etc., are both mixed with a polyamide matrix, It was not always sufficient in suppressing the decrease in transparency during film stretching.

JP-A-5-194851 discloses an organically modified layered silicate in which an organic onium ion or a silane compound having reactivity with a functional group contained in a polyarylene sulfide molecule is ionic or covalently bonded, respectively. ,
A resin composition obtained by contacting and reacting with a polyarylene sulfide is disclosed. When such contact and reaction are carried out in a polyarylene sulfide solution, the silicate layer is uniformly dispersed and the mechanical strength, elastic modulus and heat distortion temperature rise, but the reaction in such a solution causes melting. Not only may the viscosity increase, but the dispersibility was insufficient when the organically modified layered silicate was dispersed under solvent-free conditions such as melt-kneading.

[0007]

As described above, it has been proposed to use various inorganic fillers for the purpose of improving the strength and rigidity of the thermoplastic resin, but the toughness of the material can always be maintained. In addition, there is still a demand for improvement of melt flowability, and in terms of improvement of dimensional accuracy, there is still a problem of anisotropy particularly in blending of fibrous filler. It was difficult to achieve both improvement of strength and rigidity and maintenance of transparency. The object of the present invention is a thermoplastic resin having excellent strength and rigidity as well as toughness, particularly excellent ductility, a small increase in specific gravity, excellent molding surface appearance and melt flowability, and isotropically improved dimensional accuracy. Another object of the present invention is to provide a thermoplastic aromatic polycarbonate resin composition containing a composition and a layered silicate having excellent mechanical strength, rigidity, toughness, moldability, and transparency.

[0008]

The present invention has been made to solve the above problems, and its gist is to use an organic onium ion with a cation exchange layered silicate having a reactive functional group as a host. As a guest, and a thermoplastic resin capable of reacting with the reactive functional group, and the interlayer compound is contained in an amount of 0.1 to 20% by weight as an inorganic ash content. And a thermoplastic resin composition containing an aromatic polycarbonate resin and a layered silicate, wherein the amount of inorganic ash in the thermoplastic resin composition is 0.25 to 10% by weight. The product of the parallel transmittance P (%) of parallel visible light and the amount of inorganic ash A (% by weight) for a molded product made of the composition and having a thickness of 3 mm is represented by the following formula a.

[0009]

## EQU00002 ## A thermoplastic resin composition characterized by satisfying P.times.A.gtoreq.20 (a). Hereinafter, the present invention will be described in more detail. The thermoplastic resin capable of reacting with the reactive functional group of the layered silicate in the present invention (hereinafter, also referred to as a reactive thermoplastic resin) is a functional resin in any mixing process with the layered silicate having a reactive functional group. If it can react with a group, its type, composition,
There is no particular limitation such as the presence or absence of phase separation. Table 1 shows examples of combinations of the reactive functional group and the reactive thermoplastic resin component capable of reacting with the reactive functional group in the present invention.

[0010]

[Table 1] Table-1 ──────────────────────────────────── Organic functional group: Reactive heat Plastic resin ──────────────────────────────────── Amino group; Acid-modified PPO / PO / PSt -Based resins, PAR resins Epoxy resins, polyamide resins, aromatic polyester resins, acrylic resins, PC resins Epoxy groups; Polyamide resins, acid-modified PPO / PO / PSt-based resins, PAR resins, aromatic polyester resins, phenoxy Resin, Epoxy resin, PPE resin, PAS resin, PC resin Carboxyl group; Epoxy-modified PPE / PO / PSt resins, epoxy resin, polyamide resin, aromatic polyester resin, phenoxy resin, PAR resin, PPE resin , P S resin, PC resin mercapto group; epoxy-modified PPE / PO / PSt based resins, epoxy resin, polyamide resin, aromatic polyester resin, PAR resin, PPE resin, acrylic resin, PC resin carbon-carbon; Polybutadiene, polyisoprene, PPE resin, PO resin unsaturated bond acrylic resin, PAS resin nitro group; PAS resin alkoxylyl group; polyamide resin, aromatic polyester resin, PAR resin, PC resin, phenoxy resin, epoxy resin, PPE resin, PAS resin ──────────────────────────────────── PPE resin: Polyphenylene ether resin PO resin: Polyolefin resin PSt Resin: Polystyrene resin (eg ABS resin, polystyrene resin, styrene elastomer Mer, etc.) PAR resin: polyarylate resin PC resin: aromatic polycarbonate resin PAS Resin: polyarylene sulfide resin

Of these combinations, it is preferable to use an amino group, an epoxy group, a carboxyl group, or a mercapto group as a reactive functional group from the viewpoint of its effect and applicability to a wide range of thermoplastic resin matrices, and further easy reaction. It is more preferable to use an amino group and / or an epoxy group from the viewpoint of properties. Further, as a thermoplastic resin capable of reacting with a reactive functional group, from the viewpoint of improving reactivity and mechanical properties, polyamide resin, polyphenylene ether resin, aromatic polyester resin, polyarylene sulfide resin, acid-modified polyolefin resin, aromatic resin Examples thereof include polycarbonate resin.

As the polyamide resin in the present invention,
It is a polymer that contains an amide bond (-NHCO-) in the main chain and can be melted by heating. Suitable polyamide resins include polytetramethylene adipamide (nylon 46), polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodeca. Mido (nylon 612), polyundecanolactam (nylon 11), polydodecanolactam (nylon 12), polyamide obtained from terephthalic acid and / or isophthalic acid and hexamethylenediamine, from adipic acid and metaxylylenediamine The polyamide obtained, the polyamide obtained from terephthalic acid, adipic acid and hexamethylenediamine, the copolymerized polyamide containing a dimerized fatty acid as a copolymerization component, and the polyamide containing at least two different polyamide forming components among these. Such as amide copolymer and mixtures thereof. Of these, nylon 6 and nylon 66 are particularly suitable because they have excellent balance between toughness and rigidity. The starting materials for such polyamides are diamines and dicarboxylic acids, lactams or polymerizable ω-amino acids, salts of diamines and dicarboxylic acids, and oligomers of these starting materials. A specific example of such a polyamide raw material is Japanese Patent Application No. 5-24519.
As described in detail in No. 9 and the like, diamines include aliphatic diamines such as tetramethylenediamine and hexamethylenediamine, xylylenediamines, and dicarboxylic acids such as adipic acid and sebacic acid. Aromatic dicarboxylic acids such as dicarboxylic acid, terephthalic acid and isophthalic acid, dimerized fatty acids and the like, lactams such as caprolactam, undecanolactam and dodecanolactam, and polymerizable ω-amino acids are 6 -Aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like are mentioned as typical ones. These various polyamide resins or polyamide raw materials may be used in combination. The molecular weight of these polyamide resins is not particularly limited, but the relative viscosity η _rel at 25 ° C. in a concentrated sulfuric acid solution having a concentration of 1 g / dl is usually 0.9.
Is about 6.0, and preferably 1.
It is 0 to 5.0.

The polyphenylene ether resin in the present invention is a polymer in which benzene ring residues are linked via an ether bond and can be heated and melted. These are produced by a known method, for example, oxidative coupling polymerization with oxygen or an oxygen-containing gas using an oxidative coupling catalyst, using a phenol or a reactive derivative thereof as a raw material. Specific examples of the phenols and the polymerization catalyst are described in detail, for example, in JP-A-4-239029,
Typical phenols include phenol, o-cresol, 2,6-xylenol, 2,5-xylenol,
Examples include methylphenols such as 2,3,6-trimethylphenol and the like, and these phenols may be used alone or in combination of two or more kinds. The most common polyphenylene ether resin is poly (2,6-
Examples thereof include dimethyl-1,4-phenylene) ether and copolymers having a main structure thereof, but a mixture containing two or more polyphenylene ether resins can also be used. It is also possible to make a compatible mixture containing a polystyrene resin for the purpose of improving the melt fluidity without departing from the object of the present invention. The molecular weight of the polyphenylene ether resin used in the first invention is not particularly limited, but the intrinsic viscosity [η] of a chloroform solution having a concentration of 0.6 g / dl at 25 ° C. is usually 0.2 to 0.6 dl / g. And more preferably from 0.35 to 0.55 dl from the viewpoint of toughness and formability.
/ G.

The aromatic polyester resin in the present invention is a polyester having an aromatic ring in the main chain obtained by a condensation reaction of a dicarboxylic acid or its ester-forming derivative with a diol or its ester-forming derivative. Specific examples of the aromatic polyester raw material and the aromatic polyester are described in, for example, JP-A-5-2452.
As described in detail in JP-A-00-00, typical dicarboxylic acids as raw materials are terephthalic acid, isophthalic acid, 2,
Examples of the aromatic dicarboxylic acid such as 6-naphthalenedicarboxylic acid and the diol include ethylene glycol, 1,4-butanediol, cyclohexanedimethanol, cyclohexanediol, and long-chain glycol having a molecular weight of 400 to 6,000. Listed as typical aromatic polyesters are polyalkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate, polycyclohexane dimethylene terephthalate, poly (ethylene terephthalate / ethylene isophthalate) copolymers, poly (butylene terephthalate / butylene isophthalate). Examples include polyalkylene phthalates such as copolymers, polyethylene naphthalates, polyalkylene naphthalates such as polybutylene naphthalates, and the like. Among these, what is preferably used in the present invention is
Polyethylene terephthalate, polybutylene terephthalate, polycyclohexane dimethylene terephthalate and other polyalkylene terephthalates, polyethylene naphthalate, polybutylene naphthalate and other polyalkylene naphthalates, most preferably polyethylene terephthalate and polybutylene terephthalate is there. The molecular weight of the aromatic polyester used in the present invention is not particularly limited, but usually a mixed solvent of phenol and tetrachloroethane in a weight ratio of 1: 1 is used and the concentration is 1 g.
/ Dl and the intrinsic viscosity [η] measured at 30 ° C is 0.5 to
It is in the range of 3.5, and more preferably in the range of 0.7 to 2.5 in terms of toughness and moldability.

The polyarylene sulfide resin in the present invention is a polymer in which an aromatic residue is bonded through a thioether bond and is a resin which can be heated and melted. Specific examples of such a polymer structure and a production method are described in, for example, Japanese Patent Application Laid-Open No.
As described in detail in Japanese Patent Laid-Open No. 194851, the main chain structures preferably used in the present invention are polyphenylene sulfide (the following formula b) and polyphenylene sulfide sulfone (the following formula c). Here, Ph is a phenylene group, m
And n are natural numbers meaning repetition of each structure, and each repeating unit represented by m and n in the formula c may be either a random array or an array constituting a block.

[0016]

## STR1 ## - (- S-Ph-) n- (b) - (- S-Ph-) m - (- SO 2 -Ph-) n- (c)

The molecular weight of the polyarylene sulfide resin used in the present invention is not particularly limited, but it is usually in the range of 10,000 to 500,000 in terms of weight average molecular weight, and more preferably from the viewpoint of toughness and moldability. 30,00
It is in the range of 0 to 300,000. The weight average molecular weight can be determined by gel permeation chromatography (GPC), and for example, in the case of polyphenylene sulfide, 1-chloronaphthalene can be used as a developing solvent.

As the acid-modified polyolefin resin in the present invention, a polyolefin skeleton such as polyethylene,
Polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, polyisoprene, ethylene-isoprene copolymer and the like are grafted with a carboxyl group-containing compound or copolymerized with unsaturated carboxylic acids. The grafting of the carboxyl group-containing compound is carried out by a known method, for example, by melt mixing an unsaturated carboxylic acid and / or its anhydride in the presence of an organic peroxide. Suitable unsaturated carboxylic acids include maleic anhydride, maleic acid,
Examples include fumaric acid, itaconic acid, acrylic acid, methacrylic acid, crotonic acid and the like. Examples of the polyolefin skeleton preferably used in the first invention include polyethylene, polypropylene, ethylene-propylene copolymer, and ethylene-butene copolymer in terms of balance between toughness and rigidity. The method of introducing a carboxyl group which is preferable from the viewpoint of ease of production is a graft reaction by melt mixing maleic anhydride in the presence of an organic peroxide. For example, in the case of maleic anhydride grafting, the grafted amount can be determined by quantitatively determining the absorption intensity derived from the carboxyl group by infrared absorption spectrum (IR) after extracting and removing unreacted maleic anhydride with a suitable solvent such as acetone, 0.01 to 0.8% by weight, preferably 0.03 to 0.8% by weight from the viewpoint of reactivity,
The content is more preferably 0.03 to 0.6% by weight, and most preferably 0.05 to 0.5% by weight from the viewpoint of suppressing deterioration of the polyolefin skeleton such as crosslinking and molecular chain cutting.

As the aromatic polycarbonate resin in the present invention, one or more kinds of bisphenols which may contain polyhydric phenols as a copolymerization component, and carbonic acid esters such as bisalkyl carbonate, bisaryl carbonate and phosgene. It is produced by the reaction of. Specific examples of bisphenols include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) propane, 2,2-) propane. , 2,2-bis (4
-Hydroxyphenyl) propane or bisphenol A, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane , 2,2-bis (4-hydroxyphenyl)
Hexane, 2,2-bis (4-hydroxyphenyl)-
4-methylpentane, 1,1-bis (4-hydroxyphenyl)

Cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxy-3-methylphenyl) methane, bis (4-hydroxy-3-methylphenyl) phenylmethane, 1,1- Bis (4-hydroxy-3-methylphenyl) ethane,
2,2-bis (4-hydroxy-3-methylphenyl)
Propane, 2,2-bis (4-hydroxy-3-ethylphenyl) propane, 2,2-bis (4-hydroxy-)
3-isopropylphenyl) propane, 2,2-bis (4-hydroxy-3-sec-butylphenyl) propane, 2,2-bis (4-hydroxy-3-sec-butylphenyl) propane, bis (4-hydroxy) Phenyl) phenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -1-phenylpropane, bis (4
-Hydroxyphenyl) diphenylmethane, bis (4-
Hydroxyphenyl) dibenzylmethane, 4,4′-dihydroxydiphenyl ether,

4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide,
4,4'-dihydroxybenzophenone, phenolphthalein and the like can be mentioned. Typical of these are bisphenol A, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-). Hydroxy-3-methylphenyl) propane and the like, and most commonly bisphenol A is used. Polyhydric phenols are used as a copolymerization component for the purpose of changing the rheological properties of aromatic polycarbonate resins and improving the surface wear properties. For example, 1,1,1-tris (4-hydroxyphenyl) ethane and the like are used. Examples thereof include trisphenols. The method for producing the aromatic polycarbonate resin used in the present invention is not limited, but an organic solvent and an alkaline water which dissolve the produced polymer from an alkali metal salt of bisphenol and a carbonate derivative active in nucleophilic attack as raw materials Interfacial polymerization method of polycondensation reaction at the interface of bisphenols, pyridine method of polycondensation reaction of bisphenols and carbonic acid ester derivative active in nucleophilic attack in organic base such as pyridine, bisphenols and bisalkyl carbonate or bis A melt polymerization method in which a carbonic acid ester such as an aryl carbonate is used as a raw material and melt polycondensation is generally known. Examples of the carbonic acid ester derivative active in the nucleophilic attack used in the interfacial polymerization method and the pyridine method include phosgene and carbodiimidazole. Among them, phosgene is the most common because it is easily available. Specific examples of the carbonic acid ester used in the melt polymerization method are as described in detail in, for example, Japanese Patent Application No. 4-214282, and preferred examples are dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, and diphenyl carbonate. And the like diaryl carbonate.
The molecular weight of the aromatic polycarbonate resin used in the present invention is not particularly limited, but usually, in gel permeation chromatography (GPC) with a solvent of tetrahydrofuran (THF) at 40 ° C., the weight average molecular weight of polystyrene with a single molecular weight as a control is used. Mw is 15,000
0 or more, preferably 20,000 from the viewpoint of toughness and moldability.
Approximately 80,000 is suitable.

In the thermoplastic resin composition of the present invention,
Two or more reactive thermoplastic resins may be contained, and a thermoplastic resin that does not react with a reactive functional group may be contained. The total content of the reactive thermoplastic resin in the thermoplastic resin matrix in the thermoplastic resin composition is usually 30-.
100% by weight, preferably 50 to 1 from the viewpoint of improving rigidity
The amount is 00% by weight, more preferably 60 to 100% by weight.

As the thermoplastic resin other than the reactive thermoplastic resin in the thermoplastic resin matrix, any thermoplastic resin or thermoplastic elastomer can be used as needed as long as the object of the present invention is not impaired. For example, polyethylene resin, polypropylene resin, polystyrene resin, polyamide resin, aromatic polyester resin, aromatic polycarbonate resin, polyarylate resin, ABS resin, polyphenylene ether resin, polyarylene sulfide resin, epoxy resin, phenoxy resin, maleic anhydride are used together. Polymerized polystyrene resin, polystyrene resin modified with an epoxy group-containing compound, aromatic polycarbonate-polysiloxane copolymer, ethylene-
α-olefin copolymer, isoprene rubber, butadiene rubber, polystyrene-polybutadiene block copolymer (SBS), polystyrene-hydrogenated polybutadiene block copolymer (SEBS), polystyrene-poly (ethylene-propylene) block copolymer (SEP) ), Polyamide elastomers, polyester elastomers, styrene-based thermoplastic elastomers such as SBS, SEBS, and SEP modified with a compound having an acid anhydride group or an epoxy group, acrylic rubber, core-shell type acrylic rubber, MBS rubber, and the like. To be

As the cation-exchange layered silicate in the present invention, a 2: 1 structure in which an octahedral sheet structure containing Al, Mg, Li and the like is sandwiched between two SO ₄ tetrahedral sheet structures is used.
A mold is preferable, and the thickness of one layer which is a unit structure thereof is usually about 9.5 angstrom. Specifically, smectite clay minerals such as montmorillonite, hectorite, fluorohectorite, saponite, beidellite, and stevensite, Li-type fluoroteniolite, Na-type fluoroteniolite, Na-type tetrasilicon-fluorine mica, Li-type tetrasilicon-fluorine mica, etc. Examples of the swelling synthetic mica, vermiculite, fluorine vermiculite, halloysite, etc. may be natural or synthetic.

The cation exchange capacity (CEC) of these cation-exchange layered silicates is usually 30 meq / 100 g.
However, preferably 50 meq / 100 g or more,
More preferably, it is 70 meq / 100 g or more. The cation exchange capacity is measured by determining the amount of methylene blue adsorbed. If the cation exchange capacity is less than 30 meq / 100 g, the intercalation amount of the organic onium ion between layers becomes insufficient, the dispersibility in the thermoplastic resin decreases, and the strength and rigidity of the thermoplastic resin composition increase. Is not sufficient and the appearance of the molded surface is also poor. Among these layered silicates due to their cation exchange capacity and availability, smectite clay minerals such as montmorillonite and hectorite, Li-type fluorine teniolite, N
Swelling synthetic mica such as a-type fluorine teniolite and Na-type tetrasilicon fluorine mica is preferably used, and in particular, montmorillonite obtained by refining bentonite is easy to obtain, in terms of purity, Li-type fluorine teniolite (the following formula: d), swelling fluoromica such as Na-type fluoroteniolite (the following formula e) and Na-type tetrasilicon fluoromica (the following formula f) are most suitable for the present invention. The expressions d, e, and f show ideal compositions, and it is not necessary that they exactly match.

[0026]

Embedded image LiMg ₂ Li (Si ₄ O ₁₀ ) F ₂ (d) NaMg ₂ Li (Si ₄ O ₁₀ ) F ₂ (e) NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ (f)

The layered silicate having a reactive functional group and the cation exchange layered silicate having a reactive functional group in the present invention are silanol groups (-Si-) contained in the layered silicate.
By contacting a layered silicate with a compound (hereinafter, referred to as a functionalizing agent) having both a structure having reactivity with OH) and a reactive functional group such as an amino group, an epoxy group, a carboxyl group, and a mercapto group Manufactured.

As a structure having reactivity with a silanol group, a halogen-silicon bond such as a chlorine-silicon bond, a bromine-silicon bond or an iodine-silicon bond represented by the following general formula g, and an alkoxy represented by the following general formula h. -Boron bond, alkoxy-aluminum bond, alkoxy-silicon bond, alkoxy-titanium bond, alkoxy-germanium bond, alkoxy-zirconium bond, alkoxy-tin bond,
Examples thereof include a hydrolyzable oxygen-metal bond such as an alkoxy-lead bond and a silicon-nitrogen-silicon bond represented by the following general formula i.

[0029]

Embedded image X—Si (g) R—O—M (h) Si—HN—Si (i)

Here, X in the formula g represents a halogen atom, and X in the formula h
R is usually an alkyl group having 6 or less carbon atoms, preferably an alkyl group having 4 or less carbon atoms, more preferably a methyl group or an ethyl group, and M is boron, aluminum, silicon, titanium, germanium, zirconium, tin or lead. Represents one of the elements. Among these structures, a chlorine-silicon bond, an alkoxy-silicon bond, and a silicon-nitrogen-silicon bond are preferable, and an alkoxy-silicon bond is most preferable, from the viewpoints of structural stability, easy handling, and economical efficiency.

Specific examples of the functionalizing agent having such a structure include those having a chlorine-silicon bond, and 3-
Glycidyloxypropyl dimethylchlorosilane, β-
Chlorosilanes having an epoxy group such as (3,4-epoxycyclohexyl) ethyldimethylchlorosilane, 3-glycidyloxypropyltrichlorosilane, trichlorosilylacetic acid, 3-trichlorosilylpropionic acid,
Chlorosilanes having a carboxyl group such as 5-carboxyhexyldimethylchlorosilane, mercapto group-containing chlorosilanes such as 3-mercaptopropyldimetrichlorosilane, 3-mercaptopropyltrichlorosilane and 4-mercaptophenyldimethylchlorosilane,
3-methacryloxypropyldimethylchlorosilane, dimethylvinylchlorosilane, allyldimethylchlorosilane, 5-hexenyldimethylchlorosilane, 7-octenyldimethylchlorosilane, 4-vinylphenyldimethylchlorosilane, vinyltrichlorosilane, allyltrichlorosilane, 3-methacryloxypropyltrisilane Examples thereof include chlorosilanes having a carbon-carbon unsaturated bond such as chlorosilane, nitrosilanes having a nitro group such as 3-nitropropyldimethylchlorosilane, 4-nitrophenyldimethylchlorosilane, and 3-nitropropyltrichlorosilane. As those having an alkoxy oxygen-silicon bond, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyl Epoxy groups such as alkoxysilanes having an amino group such as dimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. Alkoxysilanes having, mercapto group-containing alkoxysilanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, tris (2-methoxyethoxy) vinylsilane, vinyltriethoxysilane, and vinylto Alkoxysilanes having a carbon-carbon unsaturated bond such as methoxysilane, 3-methacryloxypropyltrimethoxysilane and vinylmethyldiethoxysilane, and nitro groups such as 3-nitropropyltriethoxysilane and 3-nitropropyltrimethoxysilane. And alkoxysilanes such as tetraethoxysilane and the like. As those having a silicon-nitrogen-silicon bond, 1,3-bis (3-aminopropyl) -1,1,
3,3-tetramethyldisilazane, 1,3-bis (3-
Glycidyloxypropyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis (3-mercaptopropyl) -1,1,3,3-tetramethyldisilazane,
Examples of the disilazanes include 1,3-divinyl-1,1,3,3-tetramethyldisilazane.

The method of contacting these functionalized agents with the layered silicate is not particularly limited, but it is usually carried out by mixing without solvent or in a polar solvent, and the mixing temperature is used for the purpose of improving the introduction efficiency of the agent. In some cases it may be preferable to increase. In any case, anhydrous conditions are desirable in order to prevent excessive hydrolysis of the functionalizing agent. When a polar solvent is used, it is preferable to select an inert polar solvent in which the functional group reactive with the thermoplastic resin contained in the functionalizing agent is not easily affected. Such preferable polar solvents include amide solvents such as dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone (NMP), sulfoxides such as dimethylsulfoxide (DMSO), tetrahydrofuran, 1,4 -Cyclic ethers such as dioxane are generally used, and when the functionalizing agent does not have an acidic group such as a carboxyl group, methyl groups such as pyridine, 2-methylpyridine, 3-methylpyridine and 4-methylpyridine are further used. Pyridines, 2,3-dimethylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 3,4-
Dimethylpyridines such as dimethylpyridine, dialkylaminopyridines such as N, N-dimethylaminopyridine and N, N-diethylaminopyridine, quinoline,

Heterocyclic nitrogen-containing compounds such as quinolines such as isoquinoline can also be used. Among these, amide solvents such as DMF and DMA, and DMSO are preferably used in terms of the introduction efficiency of the functionalizing agent. When these polar solvents are used, swelling of the layered silicate may occur and the introduction efficiency of the functionalizing agent may be improved, but under extremely severe conditions,
For example, when mixing at a high temperature of 150 ° C. or higher for a long time, adverse effects such as decomposition of reactive functional groups may be observed. Usually, the mixing temperature is about room temperature to 120 ° C., and the reaction time is about 30 minutes to 48 hours, preferably about 1 hour to 24 hours. The functionalizing agent and the layered silicate can be contacted with each other by suspension stirring in a polar solvent with a stirring blade, mechanical stirring and mixing with various mills without solvent, various mixers, etc., and compression contact with rolls after impregnation without solvent. Etc. can be illustrated. These functionalizing agents may be used alone or in combination of two or more.

The organic onium ion in the present invention is represented by ammonium ion, phosphonium ion, sulfonium ion and onium ion derived from a heteroaromatic ring. The role of the onium ion structure in the present invention is to introduce an organic compound between the layers of the negatively charged silicate layer, and the kind thereof is not particularly limited. Of these, ammonium ions, phosphonium ions and onium ions derived from a heteroaromatic ring are preferable from the viewpoints of easy availability and stability.

As ammonium ions, dodecyl ammonium, hexadecyl ammonium, octadecyl ammonium, [PEG] ammonium (hereinafter [PE]
G] represents a polyethylene glycol chain) and the like, and 2 such as methyl dodecyl ammonium, butyl dodecyl ammonium, methyl octadecyl ammonium, methyl [PEG] ammonium, dodecyl [PEG] ammonium, hexadecyl [PEG] ammonium and the like.
Grade ammonium, dimethyl dodecyl ammonium, dimethyl hexadecyl ammonium, dimethyl octadecyl ammonium, diphenyl dodecyl ammonium, diphenyl octadecyl ammonium, dimethyl [PEG]
Ammonium, methyldodecyl [PEG] ammonium, methyloctadecyl [PEG] ammonium, methylbis [PEG] ammonium, dodecylbis [PEG]
Ammonium, tertiary ammonium such as hexadecylbis [PEG] ammonium, tetraethylammonium,
Quaternary ammonium having the same alkyl group such as tetrabutyl ammonium tetraoctyl ammonium, trimethyl octyl ammonium, trimethyl decyl ammonium, trimethyl dodecyl ammonium, trimethyl tetradecyl ammonium, trimethyl hexadecyl ammonium, trimethyl octadecyl ammonium, trimethyl eicosanyl ammonium, Trimethylalkylammonium such as trimethyloctadecenylammonium, trimethyloctadecadienylammonium, triethyldodecylammonium, triethyltetradecylammonium, triethylhexadecylammonium, triethylalkylammonium such as triethyloctadecylammonium, tributyldodecylammonium, tributyltedecammonium Tributylalkylammonium such as radecylammonium, tributylhexadecylammonium, tributyloctadecylammonium, dimethyldioctylammonium, dimethyldidecylammonium, dimethylditetradecylammonium, dimethyldihexadecylammonium, dimethyldioctadecylammonium, dimethyldioctadecenyl Ammonium, dimethyldialkylammonium such as dimethyldioctadecadienylammonium, diethyldidodecylammonium, diethylditetradecylammonium,
Diethyldialkylammonium such as diethyldihexadecylammonium, diethyldioctadecylammonium, dibutyldidodecylammonium, dibutylditetradecylammonium, dibutyldihexadecylammonium, dibutyldialkylammonium such as dibutyldioctadecylammonium, methylbenzyldihexadecylammonium, etc. Dibenzyldialkylammonium such as methylbenzyldialkylammonium, dibenzyldihexadecylammonium, trioctylmethylammonium, tridodecylmethylammonium,
Trialkylmethylammonium such as tritetradecylmethylammonium, trialkylethylammonium such as trioctylethylammonium, tridodecylethylammonium, trialkylbutylammonium such as trioctylbutylammonium, tridodecylbutylammonium, fragrance such as trimethylbenzylammonium A quaternary ammonium having a ring, a quaternary ammonium derived from an aromatic amine such as trimethylphenylammonium, a [PEG] -containing quaternary ammonium represented by the following formula j (in the formulas j and k,

R1 and R2 independently represent an alkyl group having 18 or less carbon atoms, m and n> 1, and 2 <m + n.
<60, preferably 10 ≦ m + n <30. ), Specifically, dimethylbis [PEG] ammonium, diethylbis [PEG] ammonium, dibutylbis [PE]
G] ammonium, methylethylbis [PEG] ammonium, methyldodecylbis [PEG] ammonium,
Ions such as dialkylbis [PEG] ammonium such as methyloctadecylbis [PEG] ammonium are tetrabutylphosphonium, tetraoctylphosphonium, trimethyldecylphosphonium, trimethyldodecylphosphonium, trimethylhexadecylphosphonium, trimethyloctadecylphosphonium, as phosphonium ions. Alkyl quaternary phosphonium such as tributyldodecylphosphonium, tributylhexadecylphosphonium and tributyloctadecylphosphonium, [PEG] -containing quaternary phosphonium represented by the above formula k,
Specifically, dimethylbis [PEG] phosphonium, diethylbis [PEG] phosphonium, dibutylbis [PE
G] phosphonium, methylethylbis [PEG] phosphonium, methyldodecylbis [PEG] phosphonium,
Ion such as dialkylbis [PEG] phosphonium such as methyloctadecylbis [PEG] phosphonium and the onium ion derived from the heteroaromatic ring include ions such as pyridinium, methylpyridinium, dimethylpyridinium, quinolinium and isoquinolinium.

[0037]

[Chemical 4]

Among these organic onium ions, trimethyldodecylammonium, trimethyltetradecylammonium, trimethylhexadecylammonium, trimethyloctadecylammonium, and triethyldodecylammonium are considered in terms of the effectiveness of the hydrocarbon structure that contributes to the hydrophobicity between silicate layers. , Quaternary ammonium having one or more alkyl groups having 12 or more carbon atoms in one molecule such as triethyltetradecylammonium, triethylhexadecylammonium, triethyloctadecylammonium, dimethyldidodecylammonium, dimethylditetradecylammonium, dimethyldihexadecyl Ammonium, dimethyldioctadecyl ammonium, diethyl didodecyl ammonium, diethyl ditetradecyl ammonium,

Quaternary ammonium having two alkyl groups having 12 or more carbon atoms in one molecule such as diethyldihexadecylammonium, diethyldioctadecylammonium, trimethyldodecylphosphonium, trimethylhexadecylphosphonium, trimethyloctadecylphosphonium, tributyldodecylphosphonium. Having an alkyl group having 12 or more carbon atoms such as tributylhexadecylphosphonium and tributyloctadecylphosphonium 4
Ions such as primary phosphonium are preferably used. Among them, carbons such as quaternary ammonium having one alkyl group having 16 or more carbon atoms in one molecule such as trimethylhexadecyl ammonium, trimethyl octadecyl ammonium, dimethyl ditetradecyl ammonium, dimethyl dihexadecyl ammonium, dimethyl dioctadecyl ammonium, etc. Quaternary ammonium having two or more alkyl groups having 14 or more carbon atoms in one molecule, trimethylhexadecylphosphonium, trimethyloctadecylphosphonium, tributylhexadecylphosphonium, tributyloctadecylphosphonium, etc. quaternary phosphonium having an alkyl group having 14 or more carbon atoms, etc. Are more preferably used from the viewpoint of maintaining the toughness and availability of the resin composition of the present invention, and most preferably trimethyloctadecyl ammonium ion and dimethyldi Hexadecyl ammonium ion, dimethyl dioctadecyl ammonium ion, tributyl hexadecyl phosphonium ion, tributyl octadecyl phosphonium ion used. When the resin matrix is a condensation polymer such as a polyamide resin, an aromatic polyester resin, or an aromatic polycarbonate resin,
From the viewpoint of the affinity between the resin matrix and the organic onium ion, dialkylbis [PEG] ammonium ion such as dimethylbis [PEG] ammonium and methyldodecylbis [PEG] ammonium, and dimethylbis [P].
[PEG] -containing organic onium ions such as dialkylbis [PEG] phosphonium ions such as EG] phosphonium and methyldodecylbis [PEG] phosphonium are also preferably used. These organic onium ions can be used alone or as a mixture of plural kinds.

The intercalation compound having a cation-exchange layered silicate having a reactive functional group as a host and an organic onium ion as a guest in the present invention includes an introduction reaction of the reactive functional group into the layered silicate and an organic compound. A compound having intercalation (intercalation) of onium ions between layers, which is produced by a process including two reactions of ion exchange reaction between onium ions and a clay containing a negative layer lattice and exchangeable cations. means. The ion exchange reaction is
For example, Japanese Examined Patent Publication No. 61-5492 and Japanese Patent Laid-Open No. 60-42.
It can be carried out according to a known method described in, for example, Japanese Patent Application No. 451 and its preferred reaction conditions are, for example, Japanese Patent Application No.
The reaction and purification methods in the case of inserting a quaternary ammonium ion described in Japanese Patent Application No. 245199 and Japanese Patent Application No. 5-245200 can be applied.

The amount of the organic onium ion in the intercalation compound was 0.8 with respect to the cation exchange capacity of the layered silicate as a raw material.
There is no particular limitation as long as it is in the range of 2.0 to 2.0 equivalents, but it is about 1.0 to 1.3 equivalents under normal reaction conditions. When this amount is less than 0.8 equivalent, dispersibility in the matrix resin is lowered, and when it is more than 2.0 equivalent, the free compound derived from the onium ion becomes prominent and the thermal stability at the time of molding is lowered,
May cause smoke, mold contamination, odor, etc. The compounding amount of the intercalation compound is 0.1 to 50 parts by weight, preferably 0.1 to 30 parts by weight, relative to 100 parts by weight of the thermoplastic resin,
It is more preferably 0.1 to 20 parts by weight.

The water content of the intercalation compound reduces undesired side reactions such as hydrolysis during mixing particularly when a condensation resin such as a polyamide resin, an aromatic polyester resin or an aromatic polycarbonate resin is used as the matrix resin. Therefore, it is desirable to control the content to 7% by weight or less, preferably 5% by weight or less, and most preferably 3% by weight or less. If the water content exceeds 7% by weight, the molecular weight of the condensation resin may be significantly reduced due to hydrolysis, and the toughness of the composition may be significantly reduced.

The thermoplastic resin composition of the present invention has an interlayer compound in an amount of inorganic ash of usually 0.1 to 20% by weight, preferably 0.3 to 8% by weight, and more preferably from the viewpoint of maintaining toughness and reinforcing effect. Is 0.3 to 5% by weight, and most preferably 0.3 to 4% by weight in terms of ductility. Here, the amount of inorganic ash means the weight fraction of the residue obtained by completely burning off the organic component of the thermoplastic resin composition in an electric furnace at 650 ° C. When the amount of the inorganic ash is less than 0.1% by weight, the mechanical strength and elastic modulus are not significantly improved, while when it exceeds 20% by weight, the toughness is greatly reduced, which is not preferable. Also in use as a masterbatch, if the amount of the inorganic ash exceeds 20% by weight, the dispersibility of the layered silicate during diluting and mixing may be deteriorated, which is not preferable. In addition,
When an intercalation compound is added, they may be used alone or in combination. It is also possible to blend the thermoplastic composition as a so-called masterbatch and dilute and mix it to a predetermined amount of inorganic ash, and in this case, a suitable inorganic ash content of the composition is 8 to 20% by weight, masterbatch. From the viewpoint of economy of use, it is more preferably 10 to 20% by weight.

In the present invention, in the phenomenon of the exchange of the interlayer cation of the layered silicate having the cation exchange ability with the organic onium ion (intercalation of the organic onium ion), the hydrophobicity between the layers is controlled by controlling the structure of the organic onium ion. The synergistic effect of decreasing the intercalation force and increasing the interlaminar distance by intercalation of organic onium ions whose structure is controlled and controlled in structure, provides a simple means such as mechanical shearing force in molten thermoplastic resin. However, a considerable cleavage dispersion is achieved.

Moreover, the surface silanol groups are present 1:
Generally, the surface of the layered silicate is relatively hydrophilic, such as the type 1 layered silicate and the 2: 1 type layered silicate having a structure covered with -O-Si-O- bond, but it is relatively hydrophilic to the lipophilic matrix resin. Also, by introducing reaction points with the matrix resin into the silicate layer, fine dispersion and improvement of interfacial adhesion can be achieved.

An intercalation compound obtained by intercalating an organic onium ion with a layered silicate having a reagent having a functional group reactive with a matrix resin has an extremely excellent cleavage dispersibility in a wide range of thermoplastic resin matrices,
The strength and rigidity of the matrix resin can be improved extremely efficiently without significantly impairing the toughness of the matrix resin, and a low isotropic molding shrinkage ratio is exhibited in injection-molded products. In particular, a transparent matrix resin can maintain its transparency well.

A thermoplastic resin composition comprising the aromatic polycarbonate resin of the present invention and a layered silicate, wherein the layered silicate in the thermoplastic resin composition has an inorganic ash content of 0.25 to 10% by weight. %, The transparency in the thermoplastic composition is the product of the parallel transmittance P (%) of parallel visible light and the inorganic ash content A (% by weight) with respect to a molded product made of the thermoplastic resin composition and having a thickness of 3 mm. Is the following formula a

[0048]

[Formula 3] P × A ≧ 20 (a) is satisfied. The parallel transmittance P is defined as the percentage of the intensity of parallel transmitted light with respect to the intensity of parallel visible light incident in the thickness direction of a composition molded to a thickness of 3 mm. Here, the visible light has a lower limit of wavelength of 3800, as described in, for example, the Physical and Chemical Dictionary, 3rd edition (Iwanami Shoten).
~ 4000 angstrom, upper limit 7600-800
It means an electromagnetic wave of about 0 angstrom, and a parallel transmitted light ray means a light ray which is not scattered in the thermoplastic resin composition and is transmitted while being parallel to the thickness direction.

When the dispersed particle diameter of the layered silicate is smaller than the wavelength of visible light, it is considered that the incident visible light is not substantially scattered in the thermoplastic resin composition. The rate P is an amount that defines the degree of dispersion of the layered silicate. More specifically, the basic structure of layered silicate is
In the case of the 2: 1 type layered silicate, the layer has a thickness of about 10 angstroms and a side length of about 1000 angstroms, and each layer is smaller than the wavelength of visible light. Can be regarded as an amount that defines the degree of overlap in the thickness direction of the layers, that is, the degree of cleavage of the laminated structure.

There is no particular limitation on the method of molding the sample used for measuring the parallel transmittance P, but the surface needs to be smooth in order to minimize scattering of incident light on the surface. Therefore, preferable molding methods are injection molding and hot press molding. The parallel transmittance P is not particularly limited as long as it is measured by an apparatus capable of measuring the luminous intensity accurately, but for example, a commercially available turbidimeter (haze meter) can be used.

As the layered silicate in the thermoplastic resin composition containing the aromatic polycarbonate resin and the layered silicate of the present invention, talc, kaolin, mica, etc. are used in addition to the above-mentioned cation-exchangeable layered silicate. However, in view of the transparency of the resin composition, the length of one side of the layer which is the basic structure thereof is on average 1200 angstroms or less, preferably 1000 angstroms or less, more preferably 900 angstroms or less.
From the viewpoint of transparency of the resin composition, it is preferable that the resin composition is pulverized so as to have an angstrom or less. Here, the layered silicate preferably has a reactive functional group capable of reacting with an aromatic polycarbonate, and the reactive functional group is bonded to the layered silicate through a covalent bond chain containing a silicon atom, In addition, it is preferable that the cation-exchange layered silicate forms an intercalation compound in which the cation-exchange layered silicate serves as a host and the organic onium ion serves as a guest. When the layered silicate is used as an intercalation compound with an organic onium ion, the cation exchange capacity is preferably 70 meq / 100 g or more from the viewpoint of ensuring sufficient dispersibility to express transparency.

The layered silicate having a reactive functional group capable of reacting with an aromatic polycarbonate, and the reactive functional group is bonded to the layered silicate through a covalent bond chain containing a silicon atom is a reactive functional group. It is manufactured by a method similar to the method for manufacturing a cation-exchange layered silicate having A thermoplastic resin composition containing an aromatic polycarbonate resin and a layered silicate has a layered silicate content of 0.25 to 1 in terms of inorganic ash content.
0% by weight, preferably 0.25 to 5% by weight from the viewpoint of transparency, and more preferably 0.25 to 3% by weight. If the amount of the inorganic ash is less than 0.25% by weight, the mechanical strength and rigidity tend to be insufficiently improved.
If it exceeds 5% by weight, the transparency tends to deteriorate. In addition,
The definition of the amount of inorganic ash is the same as above.

Since the probability of scattering of incident light in the thermoplastic resin composition increases as the content of the layered silicate, that is, the inorganic ash content A increases, the parallel transmittance P decreases at this time. Conceivable. Therefore, the formula a contains the aromatic polycarbonate resin of the present invention and the layered silicate which does not significantly impair the transparency even when the amount of inorganic ash is increased in the range of 0.25 to 10% by weight as the amount of inorganic ash. It can be said that it exhibits the characteristics of the thermoplastic resin composition.

In the present invention, the method of mixing the intercalation compound or the layered silicate and the various thermoplastic resins is not particularly limited, but it is essential that the thermoplastic resin is mixed under mechanical shearing in the molten state. It can be added at any stage in the range. For example, in the case of a condensation resin such as a polyamide resin, an aromatic polyester resin, or an aromatic polycarbonate resin, a method of adding to a resin raw material before polymerization and stirring and mixing with progress of melt polymerization, chip formation after or during melt polymerization It is possible to use a method of adding and stirring and mixing before. In addition, a method of adding to a thermoplastic resin in any form such as powder, flakes, chips and the like after completion of polymerization and melt-mixing with a kneader such as an extruder can also be generally mixed. Among these methods, a method of mixing with a kneading machine with a thermoplastic resin in an arbitrary form after completion of the polymerization is preferable from the viewpoint of productivity, convenience and versatility. Above all, it is preferable to use a twin-screw extruder having high shear efficiency, and it is most preferable to use a twin-screw extruder with a vent capable of efficiently removing water contained in the intercalation compound. In a method for dispersing a layered silicate in a thermoplastic resin composition containing an aromatic polycarbonate resin and a layered silicate, for example, an aromatic compound in a molten state is used as an intercalation compound having a cation exchange ability by intercalating an organic onium ion. A method of mixing with a group polycarbonate resin is desirable, and it is preferable to introduce a reactive functional group such as an epoxy group into the layered silicate.

The thermoplastic resin composition of the present invention contains
As long as the purpose of the present invention is not impaired, various conventionally used additive components, for example, glass fibers, inorganic fibers such as carbon fibers, glass flakes, glass beads, inorganic powders such as mica, various plasticizers, stabilizers, coloring Agents and flame retardants can be added.

[0056]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the description of the following Examples unless it exceeds the gist. Evaluation item and measuring method-Tensile test: According to ASTM D-638. The yield strength (abbreviated as YS, unit kg / cm ² ), elastic modulus (abbreviated as TM, unit kg / cm ² ) and elongation at break (abbreviated as UE, unit%) were measured. -Surface appearance observation: The surface smoothness of injection-molded articles was compared by visual evaluation. -Light transmission characteristics: turbidity NDH-300 manufactured by Nippon Denshoku Industries Co., Ltd.
According to A, haze (turbidity) of a 3 mm thick injection-molded flat plate,
The total light transmittance and the parallel light transmittance were measured. Molding shrinkage ratio: Obtained by injection-molding a flat plate (2 mm thickness x 80 mm square) using a film gate mold with a thickness of 1 mm, and measuring the dimensions in the flow direction (MD) and the MD and vertical directions (TD). It was Melt fluidity: Evaluated from the minimum filling injection pressure (kg / cm2) during tensile test piece injection molding. Impact test: Notched IZDO impact strength of 1/8 inch thickness was measured according to ASTM D256. Layered silicates used Table 2 shows the names, mineral names and types of commercially available layered silicates used, the cation exchange capacity (abbreviated as CEC) measured by the methylene blue adsorption method, and the manufacturer.

[0057]

[Table 2] Table-2 1) Unit: milliequivalent / 100 g ──────────────────────────────────── ─ Name Mineral name Type CEC ¹⁾ Manufacturer ───────────────────────────────────── Kunipia F Montmorillonite Natural 120 Kunimine Industries Co., Ltd. ME100 Swellable Fluorine Mica Synthetic 80 Corp Chemical Co., Ltd. ────────────────────────────────── ───

Reaction of Functionalized Reagent with Layered Silicate 100 g of a commercially available layered silicate dried at 180 ° C. for one day under a nitrogen stream was sealed in a ball mill substituted with dry nitrogen. A solution prepared by dissolving 2.0 g of the functionalized reagent in 8 ml of dry acetone was added thereto in 5 portions over 15 minutes, sealed, and vigorously stirred and mixed. After adding the whole amount of the solution, stirring and mixing were continued for another 20 minutes to obtain a layered silicate in which a functionalizing agent was reacted. As the functionalizing agent, 3-glycidyloxypropyltrimethoxysilane having an epoxy group as a reactive functional group and 3-aminopropyltriethoxysilane having an amino group were used. The obtained powder is repeatedly stirred and washed by stirring and filtering with dry acetone until the functionalizing agent is not mixed in the washing solution, and vacuum-dried at 80 ° C for 24 hours, and then TG manufactured by Seiko Denshi KK -DTA (thermogravimetric analysis-differential thermal analysis) device SSC-5200H, under nitrogen stream 4 per minute
Since hydrocarbon components, and particularly nitrogen atoms in the case of aminosilane-treated products, are detected in the gas generated when the temperature is raised from 25 ° C to 500 ° C at a rate of 0 ° C, the functionalizing agent is a layered silicate. Presumed to be covalently bound to. Furthermore, when the washed and dried product of the aminosilane-treated product was suspended in ethanol with stirring and titrated with 0.01N dilute hydrochloric acid, an inflection point considered to be an amino group was recognized.

Preparation of Intercalation Compound Layered silicate or layered silicate reacted with functionalizing agent About 1
After precisely weighing 00 g, it is stirred and dispersed in 10 liters of water at room temperature,
A homogeneous suspension was obtained. The CEC of the layered silicate is 1.
A double equivalent of onium ion hydrochloride was added and stirred for 2 hours. The purified precipitated solid was filtered off, then washed with stirring in 25 liters of demineralized water, and then filtered off again. This washing and filtering operation was performed at least three times, and it was confirmed by the silver nitrate test of the washing liquid that chloride ions could not be detected. The obtained solid is air-dried for 3 to 7 days, then crushed in a mortar and further heated to 50 °
Was dried with warm air for 3 to 10 hours and pulverized again in a mortar. Drying conditions vary depending on the type of guest onium ion, but the maximum particle size is about 100 μm, and the residual water content evaluated by thermogravimetric reduction when kept at 120 ° C. for 1 hour under a nitrogen stream has a residual water content of 2-3 wt. % Was used as an index.
Examples of onium ions are dimethyldioctadecyl ammonium (abbreviated as Me ₂ (C ₁₈ ) ₂ N ⁺ ), trimethyldodecyl ammonium (abbreviated as Me ₃ C ₁₂ N ⁺ ) and tributyl hexadecyl phosphonium (abbreviated as Bu ₃ C ₁₆ P ⁺ ). ) And ammonium 12-aminododecanoate (abbreviated as 12ADA ⁺ ).

Thermoplastic resin used Nylon 6 ... Novamid 1020J (manufactured by Mitsubishi Kasei Co., Ltd., relative viscosity η _rel = 3.5 at 25 ° C. of a concentrated sulfuric acid solution having a concentration of 1 g / dl) Nylon 66 ... Zitel FE3421 (manufactured by DuPont Co., Ltd., relative viscosity η _rel = 3.0 at 25 ° C. of a concentrated sulfuric acid solution having a concentration of 1 g / dl) Amorphous amorphous nylon (abbreviated as APA) ・ ・ ・ Novamid X21 (Mitsubishi Kasei ) Made of concentrated sulfuric acid solution of 1 g / dl concentration
Polyamide resin composed of isophthalic acid, terephthalic acid, and hexamethylenediamine having relative viscosity η _rel = 2.0 at 25 ° C) Polybutylene terephthalate (abbreviated as PBT) ...
-Novado wool 5020 (manufactured by Mitsubishi Kasei Co., Ltd., 1 g / dl concentration of phenol / 1,1,2,2-tetrachloroethane (weight ratio 1: 1) mixed solution at 30 ° C, the intrinsic viscosity [η]
= 1.2 (dl / g), but the Huggins constant was 0.33. )

Polyphenylene sulfide (abbreviated as PPS) ... Ryton E0780 (manufactured by Toray Phillips Co., Ltd., weight average molecular weight by GPC Mw = 223,00)
0) Polyphenylene ether (abbreviated as PPE) ・ ・ ・ G
PPE manufactured by EM Polymer Co., Ltd. (Intrinsic viscosity [η] of a chloroform solution having a concentration of 0.6 g / dl at 25 ° C. [η] = 0.47 (dl / g), with a Huggins constant of 0.30.) Ethylene-butene copolymer ( Abbreviated as EBR) ・ ・ ・ AS
190 ° C according to TM D1238 standard, 2.16 kg / cm ²
Melt index under load is 4.0 and density is 0.
The one of 88 was used. EBR grafted with maleic anhydride (abbreviated as MEBR) ... The above EBR grafted with maleic anhydride was used. The grafted amount of maleic anhydride was 0.45% by weight, the melt index was 1.9, and the density was 0.89. Aromatic polycarbonate (abbreviated as PC) ・ ・ ・ NOVAREX 7025PJ (manufactured by Mitsubishi Kasei Co., Ltd., weight average molecular weight by GPC Mw = 45,000)

[Examples 1 to 3 and 6 to 7] An intercalation compound in which a functionalizing agent shown in Table 4 was reacted to intercalate an organic onium ion (Table 4 shows the names of layered silicates, onium ion species, And the reactive functional groups of the functionalized reagent) and nylon 6 are melt-kneaded by using a twin screw extruder TEM35B manufactured by Toshiba Machine Co., Ltd. while using a vent under the conditions of a barrel temperature setting of 280 ° C. and a screw rotation speed of 150 rpm. It was made into chips. The obtained chips were vacuum dried at 120 ° C (for one day and night), and then injection molding machine J manufactured by Japan Steel Works Ltd.
With 28SA, molding was performed under the conditions of a barrel temperature of 280 ° C., a mold surface measured temperature of 85 ° C., injection / cooling = 10/10 seconds, and maximum injection speed, to obtain a tensile test piece, a bending test piece, and a 3 mm thick flat plate, respectively. For the amount of inorganic ash, about 1.5 g of a molded piece was precisely weighed, and the weight fraction of the residue in which the organic matter was completely burned off in an electric furnace at 650 ° C. was adopted, and the amount of ash is shown in Table 4.

[Examples 4 to 5] An intercalation compound obtained by reacting the functionalized reagents shown in Table 4 with 12-aminododecanoic acid ammonium ion intercalated was prepared as ε-caprolactam / 6-aminocaproic acid = 9/1. (Weight ratio)
Was mixed with the above mixture. Then, the reaction mixture was charged into a reactor, and after nitrogen substitution, the temperature was raised to 100 ° C., melting was performed, and stirring was performed for 30 minutes to disperse the intercalation compound. Thereafter, the temperature was raised to 250 ° C., the reaction was carried out at atmospheric pressure for 2 hours, and then the pressure was reduced to 50 Torr to complete the polymerization.
The depressurization time was 2 hours in total. The composition thus produced had a very high melt viscosity in a state where the shear rate was low, and it was difficult to carry out the usual operation of extracting from the reactor. The pulverized product of the composition thus obtained was extracted with hot water to remove the water-soluble components, dried under vacuum (120 ° C., 16 hours), and subjected to injection molding.
The same evaluation as was done. In addition, a mixed solvent of m-cresol / chloroform = 3/7 (weight ratio) was used as a developing solution 4
According to gel permeation chromatography at 0 ° C. (column: PL-gel 10 μm MIXED manufactured by Tosoh Corporation), the number average degree of polymerization of the nylon 6 component was 200.

[Examples 8 to 16] The same experiment as in Example 1 was carried out on each of the thermoplastic resins shown in Table 4. However, the kneading temperature and molding conditions are as shown in Table 3 below (the injection speed was set to the maximum). The PPE and MEBR systems also measured haze and total light transmittance.

[0065]

[Table 3] Table-3 ──────────────────────────────────── Molding conditions Resin kneading temperature (℃ ) Mold surface Injection / cooling Barrel temperature (℃) Measured temperature (℃) (sec) ─────────────────────────────── ────── nylon 66 280 280 85 10/10 APA 270 260 95 20/20 PBT 260 250 88 10/10 PPS 310 300 137 20/30 PPE 310 315 102 15/15 MEBR 200 200 30 15/15 ─ ───────────────────────────────────

Comparative Example 1 Nylon 6 alone was melt extruded in the same manner as in Example 1 and evaluated in the same manner. [Comparative Example 2] The same procedure as in Example 1 was carried out except that in Example 1, Kunipia F was not treated with the functionalizing agent.

Comparative Example 3 The procedure of Example 4 was repeated, except that the layered silicate was not treated with the functionalizing agent in Example 4. Nylon 6 component has a number average degree of polymerization of 200
Met. [Comparative Example 4] The same procedure as in Example 1 was carried out except that the organic onium ion was not intercalated in Example 1.

Comparative Example 5 The procedure of Example 7 was repeated, except that the ME100 was not treated with the functionalizing agent in Example 7. [Comparative Examples 6, 8, 10, 13, 15, 17] Example 8,
In 9, 10, 12, 14, and 16, without using an intercalation compound, only the thermoplastic resin was melt-extruded in the same manner,
Similar evaluation was performed.

[Comparative Examples 7, 9, 11, 12, 14, 1
6, 18] Examples 8, 9, 10, 11, 12, 14, 1
6 was performed in the same manner except that the layered silicate was not treated with the functionalizing agent.

COMPARATIVE EXAMPLE 19 In Example 16, ME
E not grafted with maleic anhydride instead of BR
A similar experiment was performed using BR. The evaluation results of Examples 1 to 16 are shown in Table 4, and the evaluation results of Comparative Examples 1 to 19 are shown in Table 5.

[0071]

[Table 4]

[0072]

[Table 5]

[Examples 17 to 21] An intercalation compound of Me ₂ (C ₁₈ ) ₂ N ⁺ intercalated with Kunipia F having an epoxy group introduced as a reactive functional group was used as a twin screw extruder manufactured by Toshiba Machine Co., Ltd. Barrel temperature setting by TEM35B 290 ℃,
Using a vent at a screw rotation speed of 150 rpm, the mixture was melt-kneaded with PC to form chips. The obtained chips were vacuum-dried at 120 ° C (one day and night), and then barrel temperature was 280 ° C, mold surface measurement temperature was 98 ° C, injection / cooling = 15/15 seconds, using an injection molding machine J28SA manufactured by Japan Steel Works Ltd. Molded under conditions of maximum speed, tensile test piece, bending test piece, 3
mm thick flat plates were obtained respectively. The amount of inorganic ash was determined in the same manner as in Example 1.

[Comparative Examples 20 to 22] The same procedures as in Examples 17 to 21 were carried out except that the treatment of Kunipia F with epoxysilane was not carried out. [Comparative Example 23] The procedure of Example 18 was repeated, except that Me ₂ (C ₁₈ ) ₂ N ⁺ was not intercalated.

[Comparative Example 24] The procedure of Example 18 was repeated except that untreated Kunipia F was used instead of the intercalation compound. [Comparative Example 25] Only PC was melt extruded in the same manner as in Example 17, and the same evaluation was performed. The evaluation results of Examples 17 to 21 and Comparative Examples 20 to 25 are shown in Table-6. Further, for Example 18, Comparative Example 21, and Comparative Example 25, GPC
The weight average molecular weight, the minimum filling injection pressure at the time of injection molding of the tensile test piece, and the molding shrinkage ratio were measured, and the results are shown in Table 7.

[0076]

[Table 6]

[0077]

[Table 7]

[Example 22] The same melt-kneading as in Example 1 was carried out with the goal of an inorganic ash content of 20 wt%. The chips thus obtained were vacuum-dried at 120 ° C. (one day and night), and then mixed (dry blended) with chips of dried nylon 6 so that the inorganic ash content of the molded product was 2 wt%, and the same molding as in Example 1 and An evaluation was made.

[Comparative Example 26] The same experiment as in Example 22 was carried out without treating Kunipia F with epoxysilane. The evaluation results of Example 22 and Comparative Example 26 are shown in Table-8.

[0080]

[Table 8]

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[Table 9]

From Table 4 and Table 5, it can be seen that when an intercalation compound in which an organic onium ion is intercalated in a layered silicate in which a functional group reactive with a matrix resin is bonded is used, it is compared with the case where the functional group is not bonded. It is also found that the balance between strength and rigidity of the resin composition and toughness is improved, and when the molded product has transparency, the transparency is maintained well. It is also seen from Table 7 that the thermoplastic resin composition of the present invention has improved melt flowability and molding shrinkage, and has excellent moldability. Further, as shown in Table-8, it can be seen that the thermoplastic resin composition of the present invention having a large amount of inorganic ash is excellent as a master batch of layered silicate.

Further, from Table 7, the thermoplastic resin composition of the present invention using an aromatic polycarbonate as a matrix resin can be prepared, for example, by a general method (Comparative Example 24) in which an inorganic powder which is not subjected to any treatment is added. It can be seen that compared to the conventional technique (Comparative Example 23) in which the wettability with the matrix resin is improved by the silane coupling agent, the transparency is far superior even with the same amount of inorganic ash. Further, it can be seen from Table 9 that the thermoplastic resin composition of the present invention containing an aromatic polycarbonate as a matrix resin has excellent impact resistance.

[0084]

INDUSTRIAL APPLICABILITY The thermoplastic resin composition of the present invention has excellent strength and rigidity, does not impair toughness, has a small increase in specific gravity, has good molding surface properties, melt fluidity, and low molding shrinkage. It has excellent moldability. Further, particularly when a transparent thermoplastic resin typified by an aromatic polycarbonate resin is used as a matrix, excellent transparency is maintained. The thermoplastic resin composition of the present invention can be easily produced in a wide range of thermoplastic resin matrices with general-purpose equipment such as a melt kneader, and has low specific gravity, good surface appearance and melt fluidity, high strength, and high strength. Making full use of features such as rigidity, high toughness, low molding shrinkage, gas barrier property, and good transparency, various mechanical parts, automobile parts, electric / electronic parts, sheets, films,
It can be applied to packaging materials.

Claims (10)

[Claims] 1. An interlayer compound containing a cation-exchange layered silicate having a reactive functional group as a host and an organic onium ion as a guest, and a thermoplastic resin capable of reacting with the reactive functional group, The intercalation compound was used as an inorganic ash content of 0.
A thermoplastic resin composition comprising 1 to 20% by weight. 2. An interlayer compound containing a cation exchange layered silicate having a reactive functional group as a host and an organic onium ion as a guest, and a thermoplastic resin capable of reacting with the reactive functional group, The interlayer compound is a thermoplastic resin 100.
A thermoplastic resin composition comprising 0.1 to 50 parts by weight based on parts by weight. 3. The thermoplastic resin composition according to claim 1 or 2, wherein the reactive functional group is bonded to the layered silicate through a covalent bond chain containing a silicon atom. 4. The thermoplastic resin composition according to claim 1, wherein the reactive functional group is an amino group or an epoxy group. 5. A thermoplastic resin capable of reacting with a reactive functional group is a polyamide resin, an aromatic polyester resin, a polyarylene sulfide resin, a polyphenylene ether resin,
The thermoplastic resin composition according to any one of claims 1 to 4, which is either an acid-modified polyolefin resin or an aromatic polycarbonate resin. 6. A thermoplastic resin composition containing an aromatic polycarbonate resin and a layered silicate, wherein the amount of inorganic ash in the thermoplastic resin composition is 0.25 to 10% by weight, and A thermoplastic resin composition characterized in that the product of parallel transmittance P (%) of parallel visible light and an inorganic ash content A (% by weight) for a molded product of a resin composition having a thickness of 3 mm satisfies the following formula a: object. [Equation 1] P × A ≧ 20 (A) 7. The layered silicate has a reactive functional group capable of reacting with an aromatic polycarbonate, and the reactive functional group is bonded to the layered silicate via a covalent bond chain containing a silicon atom. 7. The thermoplastic resin composition according to claim 6. 8. The thermoplastic resin composition according to claim 7, wherein the reactive functional group capable of reacting with the aromatic polycarbonate is an epoxy group. 9. The layered silicate is a cation-exchangeable layered silicate, which forms an intercalation compound using the cation-exchanged layered silicate as a host and an organic onium ion as a guest. The thermoplastic resin composition according to any one of claims 6 to 8. 10. A method for producing a thermoplastic resin composition, characterized in that the components of the thermoplastic resin composition according to claim 1 are blended and melt-mixed.