JP3138025B2 - Thermoplastic resin composition - Google Patents

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 having excellent impact resistance, thermal shock resistance, moisture resistance and the like.
Seats, leather, foam sheets, industrial parts (automobiles, electrical equipment, machinery, etc.), housing materials, household goods, crates, containers for detergents, foods, kerosene, etc., gaskets, cushioning materials, strings, fibers, tubes, Hose, for water supply, for gas
Pipes for agriculture and mining and civil engineering, corrugated sheets, flat plates, gutters,
Effectively used as a material for deck materials, waterproof boards, records, anticorrosion coating materials for electric wires and steel pipes, lining materials, flooring materials, joints, telephones, shoe soles, boots, carpet packing, adhesives, substrates for various discs, etc. Can be.

[0002]

2. Description of the Related Art Conventionally, thermoplastic resins have been widely used in industry because of their excellent moldability and mechanical properties. An inorganic filler is often added to the thermoplastic resin in order to reduce costs and to improve heat resistance, thermal conductivity, electrical characteristics and the like. However, in this case, there is a major drawback in that the impact resistance, thermal shock resistance, moisture resistance and the like are deteriorated by blending the inorganic filler.

[0003]

The inventors of the present invention have conducted intensive studies to obtain a composition which has solved the above-mentioned disadvantages. As a result, the present inventors have found that a filler composed of an inorganic powder impregnated with a specific diene polymer is used. By using one, impact resistance,
It has been found that a thermoplastic resin composition having excellent thermal shock resistance, moisture resistance, etc., and also excellent heat resistance, thermal conductivity, electrical properties, etc., can be obtained. Based on this finding, the present invention has been completed. .

That is, the present invention relates to a thermoplastic resin (a)
And at least 60 mol% of the diene unit of the repeating unit is 1,
4-functional functional group-containing liquid diene polymer and / or
Or a thermoplastic resin composition comprising the hydrogenated product thereof consisting of inorganic powder impregnated with filler and (b) (however, Poriore
Inorganic filler coated with liquid rubber in fin resin, unsaturated
Add carboxylic acid or its derivative and radical generator
Remove the polyolefin resin composition obtained by mixing under heat.
Good. ) .

There are various thermoplastic resins used as the component (a) in the present invention, for example, polyvinyl chloride resins such as polyethylene, polyvinyl chloride and vinyl chloride-vinyl acetate copolymer, polypropylene, polystyrene, and the like. Acrylonitrile-butadiene-styrene resin, polyvinyl alcohol, acrylic resin, allylonitrile-styrene resin, vinylidene chloride resin, partial graft copolymer of acrylic rubber and acrylonitrile-styrene copolymer, part of EPDM rubber and acrylonitrile-styrene copolymer Graft copolymer, fibrous resin such as cellulose acetate, polybutene-1, poly-4-methylpentene-1, fluororesin, polycarbonate, polyamide resin, acetal resin, polyphenylene oxide, polybutylene terephthalate DOO, polyethylene terephthalate, polyphenylene sulfide, polyimide resins, polysulfone, polyether sulfone, wholly aromatic polyesters, mention may be made of polyarylate. In the present invention, two or more of these resins can be blended, and further, a rubber component can be blended.

Next, in the present invention, the component (b) is a functional group-containing liquid diene polymer having a repeating unit having a 1,4-diene unit structure and / or an inorganic powder impregnated with a hydride thereof. Use filler. The component (b) is obtained by impregnating an inorganic powder with a functional group-containing liquid diene polymer having a specific repeating unit and / or a hydride thereof.

Here, inorganic powders include zinc, aluminum, copper, nickel, glass spheres, glass flakes, glass fibers, carbon black (channel black, fast black, acetylene black, thermal black), carbon fibers, graphite, and asbestos. , Kaolin clay, laurite clay, talc, cassiterite, cryolite, wollastonite, diatomaceous earth, slate powder, whiting, feldspar powder, mica, gypsum, quartz powder, fine silica powder,
Atavalgite, sericite, volcanic ash, vermiculite, silica, alumina, zinc oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, molybdenum dioxide, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, barium carbonate, silicate Examples include calcium, zeolite, potassium titanate, boron nitride, boron nitrite, molybdenum disulfide, and the like. Among them, it is particularly preferable to use calcium carbonate, silica, clay and the like.

[0008] The functional group-containing liquid diene polymer impregnated in the inorganic powder and / or its hydride is defined as a compound such as a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group or an acroyl group in a molecule. It refers to a liquid diene polymer containing a functional group and / or a hydride thereof. Here, the functional group-containing liquid diene polymer or its hydride can be used as a mixture of two or more kinds. This functional group-containing liquid diene polymer can be easily produced by a known method, for example, by the following method:
A hydroxyl group-containing diene polymer can be produced.

That is, a diene monomer having 4 to 22 carbon atoms (for example, butadiene, isoprene, chloroprene,
1,3-pentadiene, cyclopentadiene, etc.) are converted to hydrogen peroxide, an azo compound having a hydroxyl group (for example, 2,2).
2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide]) or a peroxide having a hydroxyl group (eg, cyclohexanone peroxide) is used as a polymerization initiator to form a hydroxyl group by radical polymerization. A liquid diene-based polymer can be produced.

The amount of the polymerization initiator used is 100 g of the diene monomer. For example, in the case of hydrogen peroxide, it is 1.
0 to 50 g, 2,2'-azobis [2-methyl-N-
(2-hydroxyethyl) propionamide] and 5.0 to 100 g are suitable for cyclohexanone peroxide. The polymerization can be carried out without a solvent, but it is preferable to use a solvent because the reaction can be easily controlled. As the solvent, ethanol, isopropanol, n-butanol and the like are usually used. The reaction temperature is suitably from 80 to 150 ° C., and the reaction time is suitably from 0.5 to 15 hours.

A diene monomer is anionically polymerized using a catalyst such as naphthalenedilithium to produce a living polymer, and a monoepoxy compound is further reacted to obtain a hydroxyl group-containing liquid diene polymer. Can be. The polymerization can be carried out without solvent, but from the same viewpoint as in the case of radical polymerization,
It is preferable to use a solvent. As the solvent, a saturated hydrocarbon such as hexane and cyclohexane is used. The reaction temperature is suitably 50 to 100 ° C., and the reaction time is suitably 1 to 10 hours. Further, at the time of polymerization, two or more kinds of diene monomers may be used as a mixture, or the diene monomer may have a carbon number of 2 or less at a ratio of 50 mol% or less.
To 22 addition polymerizable monomers (for example, butene, pentene, styrene, α-methylstyrene, acrylonitrile, acrylic acid and its ester, methacrylic acid and its ester, vinyl chloride, vinyl acetate, acrylamide, etc.). .

After completion of the reaction, the solution is distilled under reduced pressure to remove the solvent and obtain a hydroxyl group-containing liquid diene polymer. The number average molecular weight of this hydroxyl group-containing liquid diene polymer is 300-25,000, preferably 500-1.
0000 and a hydroxyl group content of 0.1 to 10 meq /
g, preferably 0.3 to 7 meq / g. In addition, 2
A mixture of two or more kinds of liquid diene polymers having a hydroxyl group can also be used.

Next, the carboxyl group-containing liquid diene polymer is obtained by radical polymerization of the above-mentioned diene monomer using a peroxide having a carboxyl group as a polymerization initiator. Further, the epoxy group-containing liquid diene polymer is obtained by reacting the above-mentioned hydroxyl group-containing liquid diene polymer with epichlorohydrin or by epoxidizing a double bond in the liquid diene polymer with peracetic acid. Can be

Further, the isocyanate group-containing liquid diene polymer can be obtained by reacting the above-mentioned hydroxyl group-containing liquid diene polymer with an excess of a polyisocyanate compound. The acroyl group-containing liquid diene polymer is obtained by reacting the above-mentioned hydroxyl group-containing liquid diene polymer with acrylic acid.

In the present invention, a hydride of the functional group-containing liquid diene polymer as described above may be used, and may be used in place of the functional group-containing liquid diene polymer as described above. You may use together. The hydrogenation is not particularly limited, but can be carried out, for example, by a known method using a homogeneous catalyst or a heterogeneous catalyst. In particular, when excellent heat resistance and weather resistance are required, the double bond in the skeleton of the hydroxyl group-containing liquid diene polymer can be hydrogenated and used.

In the present invention, it is necessary that the diene unit of the repeating unit in the functional group-containing liquid diene polymer or its hydride as described above has a 1,4-structure, and in particular, the composition is sufficient for the composition. In order to exhibit the effect, it is necessary that 60 mol% or more, preferably 70 mol% or more of the diene unit has a 1,4-structure. Here, if the diene unit of the repeating unit does not have a 1,4-structure, it will be inferior in impact strength and moisture resistance.

In the present invention, the filler used as the component (b) can be prepared by mixing the above-mentioned functional group-containing liquid diene polymer with the above-mentioned inorganic powder and impregnating (mixing and impregnating treatment). it can. The mixing ratio at the time of preparation differs depending on the type of the inorganic powder and the functional group-containing liquid diene polymer and cannot be specified, but generally, the functional group-containing liquid diene polymer is based on 100 parts by weight of the inorganic powder. It is 10 to 200 parts by weight. When the amount of the functional group-containing liquid diene polymer is less than 10 parts by weight, the effect of impregnating the functional group-containing liquid diene polymer cannot be obtained. On the other hand, when the content of the functional group-containing liquid diene polymer is more than 200 parts by weight, the obtained compound becomes liquid and is not used as a filler.

The method for impregnating the inorganic powder with the functional group-containing liquid diene polymer is not particularly limited as long as the functional group-containing liquid diene polymer can be uniformly impregnated into the inorganic powder. . Specifically, for example, a wheel type kneader,
Ball type kneader, blade type kneader, roll type kneader,
What is necessary is just to carry out using a raii machine, a colloid mill, an omni mixer, a swing mix, an electromagnetic mixer, etc. Also, in order to achieve efficient impregnation, the functional group-containing liquid diene-based polymer is gradually added to the kneader, or an appropriate solvent is added to the functional group-containing liquid diene-based polymer to impregnate the inorganic powder. After the treatment, the solvent can be distilled off.

The above component (b) is used in an amount of 5 to 500 parts by weight, preferably 3 to 100 parts by weight of the component (a).
It is used in a proportion of 0 to 300 parts by weight. Here, if the compounding ratio of the component (b) is less than 5 parts by weight, physical properties such as impact resistance and thermal shock resistance are poor. On the other hand, if it exceeds 500 parts by weight, molding becomes difficult. .

The thermoplastic resin composition of the present invention basically comprises the above components (a) and (b). If necessary, a plasticizer, a stabilizer, an antioxidant, An ultraviolet absorber, a foaming agent, a flame retardant, an antistatic agent, a lubricant, a coloring agent, a solvent, a fungicide, an anti-termite agent, a fragrance and the like can be appropriately compounded.

The thermoplastic resin composition of the present invention can be produced by mixing and kneading a predetermined amount of the above components. There is no particular limitation on the mixing and kneading method, and the mixing and kneading methods used for ordinary thermoplastic resins, for example, mixing and kneading methods using mixing rolls, blast mills, kneaders, Banbury mixers, continuous kneaders, etc. May be selected at any time. The obtained thermoplastic resin composition is subjected to injection molding, extrusion molding, blow molding, compression molding, transfer molding, inflation molding, T-die molding, lamination molding, vacuum molding, lamination molding, rotational molding, slash molding, calendering, By molding by means such as injection, a desired molded body can be obtained. The molding conditions are selected according to the type of the thermoplastic resin composition.
At a temperature of ３００300 ° C., in the range of 0.1〜500 minutes.

[0022]

Next, the present invention will be described in detail with reference to examples.

Production Example 1 (Preparation of Hydroxy Group-Containing Liquid Isoprene Polymer) A 1 liter stainless steel pressure-resistant reaction vessel was charged with 200 g of isoprene, 40 g of a 20% hydrogen peroxide solution and 100 g of isopropanol, at a temperature of 120 ° C. and a reaction time. The reaction was performed for 2 hours. During the reaction, the pressure reached a maximum of 8 kg / cm ² G. After the reaction is over,
The reaction mixture was placed in a separatory funnel, 600 g of water was added thereto, shaken, allowed to stand for 3 hours, and then an oil layer was separated. From this oil layer, the solvent, monomer, and low-boiling components were removed at 2 mmHg,
Distillation was performed at 100 ° C. for 2 hours to obtain a liquid polyisoprene having a hydroxyl group at a molecular chain terminal (yield: 66% by weight). This had a number average molecular weight of 2240, a hydroxyl group content of 0.96 meq / g and a viscosity of 64 poise / 3.
At 0 ° C., the bromine number was 220 g / 100 g. At this time, the average number of hydroxyl groups per molecule is 2.15. Also,
^The results of the structural analysis by ¹ H-NMR were as follows: trans-1,4
The structure was 57%, the cis-1,4 structure was 33%, the 1,2 structure was 6%, and the 3,4 structure was 4%.

Production Example 2 (Preparation of filler) Light calcium carbonate (trade name: Tamapearl TP-12)
100 g (1, Okutama Industry Co., Ltd.) was collected in a 1-liter beaker. In this beaker, a hydroxyl group-containing liquid butadiene polymer (trade name: Poly bd R-15HT, manufactured by Idemitsu Atchem Co., Ltd., having a trans-1,4 structure of 60% and a cis-
(19% of 1,4 structure, 21% of 1,2 structure)
A solution dissolved in 00 milliliter (ml) of toluene was added and left at room temperature for 24 hours. Next, the content of the beaker was transferred to a 2 liter eggplant-shaped flask, and the content was adjusted at 50 ° C. and 20 mmHg using a rotary evaporator.
Evaporation was carried out for 5 hours, and further at 70 ° C. and 1 mmHg for 1.5 hours to obtain a filler.

Production Example 3 (Preparation of Filler) Production Example 2 was the same as Production Example 2, except that 25 g of the hydroxyl-containing liquid isoprene polymer obtained in Production Example 1 was used instead of the hydroxyl-containing liquid butadiene polymer. In the same manner as in Example 2, a filler was obtained.

Preparation Example 4 (Preparation of Filler) In Preparation Example 2, silica (trade name: Syloid 72, Fuji Devison Co., Ltd.) was used instead of light calcium carbonate.
100 g) and a hydroxyl group-containing liquid butadiene polymer (trade name: Poly bd R-15HT, Idemitsu Atchem Co., Ltd.)
(Trans-1,4 structure: 60%, cis-1,4 structure: 19%, 1,2 structure: 21%) except that 85 g of the same was used. Obtained.

Production Example 5 (Preparation of Filler) In Production Example 4, instead of the hydroxyl group-containing liquid butadiene polymer, an acroyl group-containing liquid butadiene polymer (trade name: Poly bd R-45-ACR-LC, Idemitsu Atchem) (stock)
), A trans-1,4 structure of 60%, a cis-1,4 structure of 20%, and a 1,2 structure of 20%). Obtained.

Preparation Example 6 (Preparation of Filler) In Preparation Example 5, 100 g of clay (trade name: SPMA clay, manufactured by Takehara Chemical Industry Co., Ltd.) was used in place of silica, and the weight of acroyl group-containing liquid butadiene was changed. Combined (Product name: Poly bd R-45-ACR-LC, Idemitsu Atchem Co., Ltd.)
), The trans-1,4 structure is 60%, the cis-1,4 structure is 20%, and the 1,2 structure is 20%). I got

Preparation Example 7 (Preparation of Filler) In Preparation Example 2, the hydroxyl group-containing liquid butadiene polymer was replaced with another hydroxyl group-containing liquid butadiene polymer (trade name:
NISSO-PB G-1000, manufactured by Nippon Soda Co., Ltd.
%, 1,2 structure is 94%) except that 25 g was used.
The procedure was performed in the same manner as in Production Example 2 to obtain a filler.

Examples 1 to 18 and Comparative Examples 1 to 12 Compounds having the compositions shown in Table 1 were kneaded using a Banbury mixer, and then injection molded to obtain test pieces. Table 1 shows the kneading conditions and the injection molding conditions. Using the obtained test pieces, Izod impact strength and moisture resistance (weight change rate) were evaluated. The results are shown in Table 1.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Table 3]

(Footnote to Table 1) * 1: Polypropylene (Product name: Sumitomo Noblen W-10)
1, melt index (MI) = 9, Sumitomo Chemical Co., Ltd.
* 2: High-density polyethylene (trade name: HIZEX 2200)
J, MI = 5, manufactured by Mitsui Petrochemical Industry Co., Ltd.) * 3: Polystyrene (trade name: Idemitsu Styrol NF20,
MI = 9, manufactured by Idemitsu Petrochemical Co., Ltd.) * 4: Izod impact strength (based on ASTM D-256, with notch) * 5: Evaluation of moisture resistance (72 at 80 ° C., 95% humidity)
* 6: Light calcium carbonate (trade name: Tamapearl TP-)
121, manufactured by Okutama Industry Co., Ltd.) * 7: Silica (trade name: Syloid 72, manufactured by Fuji Devison Co., Ltd.) * 8: Clay (trade name: SPMA clay, manufactured by Takehara Chemical Industry Co., Ltd.)

[0035]

The thermoplastic resin composition of the present invention contains, as a filler, an inorganic powder impregnated with a specific functional group-containing liquid diene polymer, and thus has impact resistance, thermal shock resistance, and moisture resistance. It has excellent properties such as heat resistance, thermal conductivity, and electrical properties. Therefore, the thermoplastic resin composition of the present invention can be widely used as a material for various films, sheets, industrial parts and the like.

Claims (1)

(57) [Claims] 1. An inorganic powder impregnated with a thermoplastic resin (a) and a functional group-containing liquid diene polymer having a 1,4-structure in which at least 60 mol% of diene units of a repeating unit have a 1,4-structure and / or a hydride thereof. Thermoplastic resin composition comprising a filler (b) consisting of a body (provided that a liquid
Rubber-coated inorganic fillers, unsaturated carboxylic acids or
Derivatives and radical generators are mixed by heating.
Excluding the polyolefin resin composition. ) .