JP2000053805A - Organic and inorganic composite, compound resin composition and preparative process thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composite which, when combined with a synthetic pesin, gives a compsn. having improved mechanical characteristics, heat resistance and light resistance without detriment to the moldability, by rendering a part of a positive charged organic compd. and a part of a light stabilizer to at least coexist between the layers of a lamellar silicate. SOLUTION: A positive-charged organic compd. is pref. one or more compds. selected from primary to tertiary amines, quaternary ammonium salts and amino acid derivatives [e.g.: dodecyl(2-hydroxyethyl)methylammonium chloride]. A photostabilizer is pref. one or more compds. selected from benophenone type substances, benzotriazole type substances, aryl esters, oxamides, formamidines and hindered amine type substances. A composite has a positive-charged organic compd. content of pref. 0.3-3 equivalents relative to a positive ion-exchanging capacity of the lamellar silicate and a photostabilizer content of pref. 0.5-5 in a mole ratio of the photostabilizer/the positive-charged organic compd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite in which an organic compound coexists between layers of a layered silicate, and an organic-inorganic composite which exhibits excellent light stability when dispersed in a synthetic resin. And a composite resin composition and a method for producing the same.

[0002]

2. Description of the Related Art Many synthetic resin materials have been developed as living materials and industrial materials and used in various places. Accompanying this, opportunities for exposure to ultraviolet rays such as sunlight and fluorescent lamps are rapidly increasing, and materials having high light stability are required. The resin material is used in combination with an inorganic filler and a light stabilizer in order to simultaneously satisfy the balance of mechanical properties, heat resistance and the like and the light stability depending on the application. recent years,
The environment in which resin materials are used is widespread, and the light stability of synthetic resins tends to be required to be longer than before.

[0003]

However, even if the amount of the light stabilizer is simply increased, the improvement of the light resistance is limited, and other resin properties are impaired. As resin materials, materials with high strength, high heat resistance and excellent moldability have been demanded, but as the amount of inorganic filler added increases, mechanical strength and heat resistance improve, but molding There is a problem that workability is reduced. The present invention has been made to solve the above problems, and has an object to improve mechanical properties and heat resistance, and also improve light resistance, without impairing the lightweight property of a thermoplastic resin and the moldability. is there.

[0004]

The present invention is characterized in that at least a part of (A) a positively charged organic compound and a part of (B) a light stabilizer coexist between layers of a layered silicate. An organic-inorganic composite is provided. Further, the present invention provides a composite resin composition containing 0.1 to 30% by weight of the organic-inorganic composite. Further, the present invention provides a method for producing an organic-inorganic composite, comprising a step of contacting a layered silicate with a positively charged organic compound, and a step of subsequently contacting the layered silicate with a light stabilizer. It also does.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The layered silicate used in the present invention is rich in changes such as chemical composition and crystal structure, and there is no established classification and nomenclature. The feature of the layered silicate mentioned here is a layered crystal, which belongs to phyllosilicate in mineralogy. In particular, consisting of two tetrahedral layers and one octahedral layer 2:
There is a 1: 1 type phyllosilicate composed of a type 1 phyllosilicate, one tetrahedral layer and one octahedral layer, and typical minerals of the 2: 1 type phyllosilicate are smectite, vermiculite, mica, and chlorite. There is kind
1: 1 type phyllosilicates include kaolin and serpentine. The smectite group includes saponite, hectorite, sauconite, montmorillonite, beidellite, nontronite, and stephensite.The vermiculite group includes trioctahedral vermiculite, dioctahedral vermiculite, and the mica group. Examples thereof include compositions such as phlogopite, biotite, lepidrite, muscobite, paragonite, chlorite, margarite, teniolite, and tetrasilicic mica. These phyllosilicates may be produced naturally or synthesized by a hydrothermal method, a melting method, a solid phase method, or the like.

[0006] Layered silicates contain ions, molecules,
It is known to insert (intercalate) clusters to form intercalation compounds. For example, by performing ion exchange between the exchangeable metal cation of the hydrophilic layered silicate and the positively charged organic compound, an interlayer compound having a controlled interlayer distance can be obtained. The obtained interlayer compound can be separated into single layers or finely dispersed while limiting the number of layers by matching the compatibility between the organic molecules between the layers and the resin material of the matrix. As a result, the following effects can be expected by compounding with a resin material. (1)
The aspect ratio of the dispersed layered silicate increases, and the heat resistance and mechanical strength of the resin material can be improved.
(2) Reduce the warpage and dimensional shrinkage of the molded body. (3)
Concealment can be provided. Further, the layered silicate can insert two or more kinds of organic molecules by intercalation. Therefore, the organic molecule for the purpose of improving the affinity with the resin material and the organic molecule for the purpose of adding the function to the resin material can be inserted together.

The type of the positively charged organic compound (A) used in the present invention is not particularly limited, but preferred examples thereof include primary amines, secondary amines, tertiary amines and their chlorides and quaternary ammonium salts. , An amine compound, an amino acid derivative, a nitrogen-containing heterocyclic compound, or a phosphonium salt. Specifically, primary amines represented by octylamine, laurylamine, tetradecylamine, hexadecylamine, stearylamine, oleylamine, acrylamine, benzylamine, aniline, etc .; dilaurylamine, ditetradecylamine, diamine Secondary amines represented by hexadecylamine, distearylamine, N-methylaniline and the like: dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine,
Dimethyl myristylamine, dimethyl palmitylamine, dimethylstearylamine, dilauryl monomethylamine, tributylamine, trioctylamine, N,
Tertiary amines represented by N-dimethylaniline and the like; tetrabutylammonium ion, tetrahexylammonium ion, dihexyldimethylammonium ion,
Dioctyldimethylammonium ion, hexatrimethylammonium ion, octatrimethylammonium ion, dodecyltrimethylammonium ion, hexadecyltrimethylammonium ion, stearyltrimethylammonium ion, docosenyltrimethylammonium ion, cetyltrimethylammonium ion, cetyltriethylammonium ion, hexadecyl Ammonium ion, tetradecyl dimethyl benzyl ammonium ion, stearyl dimethyl benzyl ammonium ion, dioleyl dimethyl ammonium ion, N-methyldiethanol lauryl ammonium ion, dipropanol monomethyl lauryl ammonium ion, dimethyl monoethanol lauryl ammonium ion, polyoxy Ethylene dodecyl monomethyl ammonium ions include quaternary ammonium and alkyl aminopropyl amine quaternized. Further, leucine, cysteine, phenylalanine, tyrosine, aspartic acid, glutamic acid, lysine, 6-aminohexylcarboxylic acid, 12-aminolaurylcarboxylic acid, N, N
-Dimethyl-6-aminohexylcarboxylic acid, Nn-
Amino acid derivatives such as dodecyl-N, N-dimethyl 10-aminodecyl carboxylic acid, dimethyl-N-12 amino lauryl carboxylic acid; pyridine, pyrimidine, pyrrole,
Imidazole, proline, γ-lactam, histidine,
Examples include nitrogen-containing heterocyclic compounds such as tryptophan and melamine.

In the present invention, the amount of the positively charged organic compound is determined based on the cation exchange capacity (hereinafter referred to as “CE”) of the layered silicate.
C ". ) Is preferably 0.3 to 3 equivalents, particularly preferably 0.1 to 3 equivalents.
5 to 2.0 equivalents are most preferred. In addition, C of layered silicate
EC differs depending on the type, locality, and composition of the layered silicate, and therefore needs to be measured in advance. Examples of the CEC measurement method include a column permeation method (Clay Handbook, 2nd edition, pages 576-577, edited by The Clay Society of Japan), a methylene blue adsorption method (Japan Bentonite Industry Association Standard Test Method, JBAS- 107-91).

The light stabilizer used in the present invention includes:
Benzophenone-based substances, benzotriazole-based substances, aromatic benzoate-based substances, dianoacrylate-based substances,
Examples include ultraviolet absorbers such as anilide-based substances and light stabilizers for hindered amine-based substances. Specifically, as an example of the ultraviolet absorber, 2- (2′-hydroxy-5 ′)
-Methyl-phenyl) benzotriazole, 2- (2 '
-Hydroxy-3 ', 5'-di-t-butyl-phenyl, benzotriazole, 2- (2'-hydroxy-
3 ′, 5′-bis- (α, α-dimethylbenzyl) phenyl) benzotriazole, 2- (2′-hydroxy-
4'-octoxyphenyl) benzotriazole, 2,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,
4'-dimethoxybenzophenone, 2-hydroxy-4
-Methoxy-5-sulfobenzophenone, 2-hydroxy-4-oxybenzophenone, pt-butylphenyl salicylate, p-octylphenyl salicylate,
2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, ethyl-2-cyano-3,3'-diphenylacrylate, ethyl-2-cyano-3,3'-
Diphenyl acrylate, N- (2-ethyl-phenyl) -N '-(2-ethoxy-5-t-butylphenyl) oxalic acid diamide, N- (2-ethyl-phenyl)-
N '-(2-ethoxy-phenyl) oxalic acid diamide and the like can be mentioned. Examples of the hindered amine light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate. , 2- (3,5
-Di-t-butyl-4-hydroxybenzyl) -2-n
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -butylmalonate, dimethyl succinate 1- (2
-Hydroxyethyl-4-hydroxy-2,2,6,6
-Tetramethylpiperidine polycondensate, poly [ポ リ 6-
(1,1,3,3-tetrabutyl) amino-1,3,5
-Triazine-2,4-diyl} (2,2,6,6-
Tetramethyl-4-piperidyl) imino {hexamethylene} (2,2,6,6-tetramethyl-4-piperidyl) imino}], N, N'-bis (3-aminopropyl) ethylenediamine.2.4 -Bis [N-butyl-N
-(1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, bis (1-octyloxy-2,2,6,6-tetra Methyl-4-piperidyl) sebacate and the like. Further, the light stabilizer may have a functional group such as a hydroxyl group, a vinyl group, an epoxy group, a mercapto group, and an isocyanate group in the structure. Further, these light stabilizers may be used alone or in combination of two or more.
The compounding amount of the light stabilizer is preferably 0.5 to 5 in terms of the light stabilizer / positive charge organic compound molar ratio, and more preferably 1.0 to 3
Is preferred.

The method for producing an organic-inorganic composite according to the present invention comprises a step of contacting a layered silicate with a positively charged organic compound, and a step of subsequently contacting the layered silicate with a light stabilizer. . In the step of contacting the layered silicate with a positively charged organic compound, by contacting the positively charged organic compound, at least a part of the positively charged organic compound is inserted between the layers of the layered silicate and ion-bonded to the silicate sheet. To form an interlayer compound. Next, a part of the light stabilizer is inserted into the intercalation compound by bringing the intercalation compound into contact with the light stabilizer.

A feature of the above-mentioned production method is that a positively charged organic compound is previously inserted between the layers of the layered silicate and then brought into contact with a light stabilizer to intervene between the layers. Light stabilizers used in synthetic resins are individually designed for molecular weight, appearance (powder or liquid), melting point, vapor pressure, etc. according to the intended resin, and generally have good compatibility with hydrophobic resins. It is. Therefore, the affinity with the organophilic (hydrophobicized) interlayer compound is also improved. As a step of bringing the interlayer compound into contact with the light stabilizer, there are a method in which the light stabilizer is contacted via an organic solvent or a low molecular weight organic compound, and a method in which the light stabilizer is contacted in a molten state. In selecting an organic solvent, it is preferable to select an organic solvent that can swell the interlayer compound indefinitely or limitedly and that dissolves the light stabilizer.

Confirmation that the positively charged organic compound and the light stabilizer coexist between the layers of the layered silicate is performed by the following method. Sample a with a positively charged organic compound inserted into a layered silicate
Then, the sample b further subjected to the light stabilizer treatment is measured for the distance between the bottom surfaces and the amount of organic components by using a powder X-ray diffraction (XRD) and a differential thermal / thermogravimetric simultaneous measurement device (TG / DTA). The light stabilizer treated sample b can be estimated from the fact that the bottom distance d (001) and the amount of organic components are further increased as compared with the sample a.

The synthetic resin used in the composite resin composition of the present invention includes a thermoplastic resin and a thermosetting resin. As the thermoplastic resin, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-vinyl acetate copolymer Styrene, such as polyolefin resins such as polystyrene, ethylene-methacrylate copolymer, ionomer resin, polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, polyacrylonitrile, and styrene-ethylene-butene terpolymer. , Acrylonitrile-based resin, halogen-containing resin such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polycarbonate, polyacetal, polyamide 6, polyamide 66, polyamide 11,
Polyamide-based resins such as polyamide 12, aromatic polyamide, polymethacrylimide and the like and copolymers thereof, polyethylene-based resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, aliphatic polyester and aromatic polyester, ethylene vinyl acetate Copolymers, ethylene-methacrylate copolymers, polyphenylene ethers, polyphenylene sulfides, polysulfone resins and the like can be mentioned. Examples of the thermosetting polymer include a urethane resin, an epoxy resin, a phenol resin, an unsaturated polyester resin, a melamine resin, and a urea resin. These may be polymer alloys of a single type or a combination of a plurality of types, and may contain other inorganic fillers such as fibrous, whisker-like, and spherical shapes.

The composite resin composition of the present invention is obtained by dispersing the organic-inorganic composite in the above synthetic resin. The content of the organic-inorganic composite in the composite resin composition is 0.1 to 30% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 20% by weight.
~ 15% by weight is preferred. When the content of the organic-inorganic composite is less than 0.1% by weight, the effects of improving light stability, mechanical strength, and heat resistance are poor. On the other hand, if it exceeds 30% by weight, the dispersion state of the organic-inorganic composite is hindered, and there is a possibility that physical properties may be deteriorated and appearance may be deteriorated.

The organic-inorganic composite can be compounded into a synthetic resin by a polymerization method in which the organic-inorganic composite is mixed into a polymerization reactor when the synthetic resin is polymerized, or by a melt kneading apparatus. There is a method of melting and kneading the resin and the organic-inorganic composite. Specific examples of the melt kneading apparatus include a continuous mixer, a Banbury mixer, a roll,
A single-screw extruder, a twin-screw extruder, a tandem-type extruder and the like can be mentioned. Further, a method of injecting a mixture of layered silicate / positive charge organic compound / light stabilizer / organic solvent using a plunger pump or the like in these melting processes may be adopted.

[0016]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, the measuring method of each physical property is shown below. CEC: Based on the column permeation method. Flexural modulus: ASTM D790 (23 ° C, bending speed)
(2.5 mm / min). Tensile strength: Measured under the conditions of ASTM D638 (23 ° C.) and a tensile speed of 10 mm / min for polyacetal resin and 50 mm / min for polypropylene resin. Heat resistance: Flexural stress of 0.185 kg / polyacetal resin in accordance with ASTM D648. mm ² (264p
si) and polypropylene resin 0.0464 kg /
It was measured under the condition of mm ² (66 psi). Light stability: A tensile test piece was taken at a temperature of 83 using a weather meter (WBL-SUN-HCH type, manufactured by Suga Test Instruments Co., Ltd.).
After irradiating at 300C for 300 hours, the tensile strength was measured and represented by the retention (%).

Production Examples Hereinafter, production examples of organic-inorganic composites will be described. As the layered silicate, tetrasilicic mica (“Somasif ME-100” manufactured by Corp Chemical Co., CEC; 107 meq / 100)
g) 200 g was dispersed in 4000 cc of distilled water and sufficiently swelled. Dodecyl (2-hydroxyethyl) methylammonium chloride (Esogard C manufactured by Lion Akzo Co., Ltd.) is used as a positively charged organic compound in this layered silicate aqueous solution.
/ 12) was added in an amount of 1.5 equivalents to CEC, and the mixture was sufficiently stirred to perform an ion exchange reaction. This suspension was filtered, washed and filtered repeatedly to remove free ammonium ions, dried and pulverized to obtain an interlayer compound. Next, an ethyl acetate suspension containing 20% by weight of this intercalation compound and an ethyl acetate solution containing 20% by weight of a hindered amine (Adecastab LA-63P) as a light stabilizer were mixed at a weight ratio of 3: 2 and stirred sufficiently. Then, the solvent was removed and pulverized to obtain an organic-inorganic composite (hereinafter referred to as “OS-1”). X-ray diffractometer (Rigaku Denki Co., Ltd.)
INT), the results were 10 ° and 19 °, respectively.
Å and 25Å. In addition, the amount of organic components contained in OS-1 was measured using a thermogravimeter (TG-D, manufactured by Seiko Instruments Inc.).
TA) and the result was 34% by weight.

The OS was the same except that a bentriazol type ultraviolet absorber (LA-31 manufactured by Asahi Denka Co., Ltd.) was used as the light stabilizer.
Organic-inorganic composite (hereinafter referred to as “OS-2”)
That. ) Got. The spacing between the bottom surfaces of OS-2 was 23 °, and the amount of the organic component was 36% by weight.

As a positively charged organic compound, distearyl dimethyl ammonium chloride (Coatamine DM manufactured by Kao Corporation)
-86P) as a hindered amine light stabilizer (CHA Specialty Chemicals CH)
OS-1 except that it was replaced by IMASSORB 944LD)
An organic-inorganic composite (hereinafter referred to as “OS-3”) was obtained in the same manner as in the above. OS-3 had a bottom surface interval of 38 ° and an organic component amount of 49% by weight.

As a light stabilizer, a benzotriazole-based ultraviolet absorber (TIA manufactured by Ciba Specialty Chemicals, Inc.)
An organic-inorganic composite (hereinafter, referred to as “OS-4”) was obtained in the same manner as in OS-3, except that the composition was changed to NUVIN327). OS-4 has a bottom spacing of 39 ° and an organic content of 48.
% By weight.

Example 1 A copolymer polyacetal resin (Duracon M90-40 manufactured by Polyplastics Co., Ltd.) was used as a synthetic resin.
-1 was blended so that the silicate component was 3% by weight, and melt-kneaded at a temperature of 190 ° C. in a twin-screw extruder (PCM30 manufactured by Ikegai Co., Ltd.) to obtain pellets. Various test pieces were prepared from the obtained pellets using a 75-ton injection molding machine with a mold clamping pressure.

Example 2 A test piece was prepared in the same manner as in Example 1 except that the organic-inorganic composite was changed to OS-2.

Comparative Example 1 Instead of an organic-inorganic composite, talc (“500 made by Hayashi Kasei Co., Ltd.”) was used.
0S ") was treated and evaluated in the same manner as in Example 1 except that 3% by weight was blended.

Comparative Example 2 In Example 1, the interlaminar compound not subjected to the light stabilizer treatment and the light stabilizer were simultaneously mixed with a polyacetal resin powder in a Henschel mixer, and the method was changed to a melt kneading method. It was injection molded and evaluated.

Example 3 As a synthetic resin, a polypropylene block copolymer H was used.
IPP (J-Allomer P manufactured by Japan Polyolefin Co., Ltd.
M771M ", MFR; 9.5 g / 10 min) and maleic anhydride-modified PP (manufactured by Nippon Polyolefin Co., Ltd., E
R320P), and a mixture (hereinafter referred to as “MB”) obtained by previously kneading OS-3 with the modified PP so as to be 30% by weight of a silicate component is obtained, and then HIPP and HI are obtained.
A compound having a PP / MB ratio of 90/10 (weight ratio) and a silicate component of 3% by weight was prepared. The obtained compound was subjected to the same treatment and evaluation as in Example 1.

Example 4 The same processing and evaluation as in Example 3 were performed except that the organic-inorganic composite was changed to OS-4.

Comparative Example 3 In Example 3, the interlaminar compound not subjected to the light stabilizer treatment and the light stabilizer were mixed together with the modified PP powder in a Henschel mixer, and the method was changed to melt kneading, and injection was performed in the same manner. It was molded and evaluated. Table 1 shows the above evaluation results.
Shown in

[0028]

[Table 1]

[0029]

The organic-inorganic composite of the present invention is useful because a composite resin composition having excellent mechanical properties and light resistance can be obtained by forming a composite with a synthetic resin.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masayuki Noguchi 3-2 Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Showa Denko KK Kawasaki Laboratory (72) Inventor Ao Ebata Kawasaki-ku, Kawasaki-shi, Kanagawa 3-2 Chidoricho Showa Denko KK Research Institute Kawasaki Laboratory F-term (reference) 4G042 AA09 4J002 AA011 AA021 BB211 BP021 CB001 DJ006 EE038 EH128 EN017 EN057 EN117 EN137 EU017 EU027 EU038 EU047 EU117 EU137 EU178 EU187 FD048

Claims (6)

[Claims] 1. An organic-inorganic composite, wherein at least a part of (A) a positively charged organic compound and a part of (B) a light stabilizer coexist between layers of the layered silicate. 2. The method according to claim 1, wherein (A) the positively charged organic compound is primary to
And at least one selected from the group consisting of quaternary amine salts, quaternary ammonium salts and amino acid derivatives.
The organic-inorganic composite according to the above. 3. The light stabilizer (B) is at least one selected from the group consisting of a benzophenone-based substance, a benzotriazole-based substance, an aryl ester, an oxanide, a formamidine, and a hindered amine-based substance.
Or the organic-inorganic composite according to claim 2. 4. The content of (A) the positively charged organic compound is 0.3 to 3 equivalents of the cation exchange capacity of the layered silicate,
The organic-inorganic composite according to any one of claims 1 to 3, wherein the content of the light stabilizer (B) is 0.5 to 5 in a molar ratio of the light stabilizer / the positively charged organic compound. 5. A composite resin composition comprising 0.1 to 30% by weight of the organic-inorganic composite according to any one of claims 1 to 4 in a synthetic resin. 6. A method for producing an organic-inorganic composite, comprising: a step of bringing a layered silicate into contact with a positively charged organic compound; and a step of bringing the layered silicate into contact with a light stabilizer.