KR20000077205A - Process for producing resin composition - Google Patents

Abstract

The present invention provides a method of preparing a resin composition comprising the following steps:

(i) compacting the resin powder containing material, thereby obtaining a compression molded material in which the resin powder is adhered to each other,

(ii) milling the compression molded material to obtain particles, and

(iii) administering the particles and one or more other materials to a melt kneading machine and melt kneading them to obtain a resin composition.

Description

How to prepare resin composition {PROCESS FOR PRODUCING RESIN COMPOSITION}

The present invention relates to a method for producing a resin composition. More particularly, the present invention relates to a method for producing a resin composition having very good productivity using a resin powder-containing material as a starting material, the material containing a large amount of resin powder having a small powder diameter.

BACKGROUND OF THE INVENTION A method of producing a resin composition by melt-kneading a resin and at least one other material with a melt-kneading machine has been widely applied.

However, when using a material containing a large amount of resin powder having a small powder diameter, there is a problem that the material introduced into the melt-kneading machine is not smoothly transported in the melt-kneading machine, and thus the productivity of the resin composition obtained Decreases extremely.

Accordingly, it is an object of the present invention to provide a method for preparing a resin composition using a material containing a large amount of a resin powder having a small powder diameter as a starting material, which method can smoothly perform a melt-kneading operation. Can provide very good productivity.

The inventors have conducted extensive studies to find out why when using a material containing a large amount of resin powder having a small powder diameter, the material introduced into the melt-kneading machine cannot be smoothly transported in the melt-kneading machine. As a result, it has been found that when using a material containing a large amount of resin powder having a small powder diameter, it cannot be successfully captured in the screw of the melt-kneading machine, whereby the melting machine is idle. The present inventors completed the present invention by conducting research to solve the above problems.

The present invention provides a method of preparing a resin composition comprising the following steps:

(i) compacting the resin powder containing material, thereby obtaining a compression molded material in which the resin powder is adhered to each other,

(ii) milling the compression molded material to obtain particles, and

(iii) administering said particles and one or more other materials to a melt-kneading machine and melt-kneading them to obtain a resin composition.

Further areas of applicability of the present invention will become apparent from the detailed description of the invention described below. However, while the detailed description and specific examples of the invention represent preferred embodiments of the invention, various changes and modifications within the scope of the invention are apparent to those skilled in the art from the detailed description of the invention and are given for illustration only. .

The resin used in step (i) of the present invention is not particularly limited. As the resin, polyphenylene ether resin; Polycarbonate resins; Examples include polyolefin resins including high density polyethylene resins, medium density polyethylene resins, low density polyethylene resins, linear low density polyethylene resins, polypropylene resins, and ethylene / propylene copolymer resins; Polyphenylene sulfide resins; And acrylonitrile / butadiene / styrene copolymer resins.

Polyphenylene ether resins are homopolymer or copolymer resins obtained by oxidative polymerization of one or more phenolic compounds represented by the following formula (1) with the aid of an oxygen or oxygen-containing gas and an oxidative coupling catalyst:

In the above formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are independently of each other a hydrogen atom, a halogen atom, a hydrocarbon group or a substituted hydrocarbon group, provided that one of them is always a hydrogen atom.

According to the production method, the obtained polyphenylene ether resin has a large amount of resin powder having a small powder diameter, for example, having a powder diameter of about 710 μm or less in an amount of 70% by weight or more based on the total weight of the resin. There is often a number containing a resin containing a resin powder. In the present invention, it is recommended to use such a resin as the resin powder-containing material for step (i).

Examples of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ in formula (1) are hydrogen, chlorine, bromine, fluorine, iodine, methyl, ethyl, n- or iso-propyl, pri-, sec- or t -Butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl, hydroxymethyl, carboxyethyl, methoxycarbonylethyl, cyanoethyl, phenyl, chlorophenyl, methylphenyl, dimethylphenyl, ethylphenyl and allyl.

Examples of the phenolic compound represented by the formula (1) include phenol, o-, m- or p-cresol, 2,6-, 2,5-, 2,4-, or 3,5-dimethylphenol, 2 -Methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-diethylphenol, 2-methyl-6-ethylphenol, 2,3,5-, 2,3,6- or 2,4 , 6-trimethylphenol, 3-methyl-6-t-butylphenol, thymol and 2-methyl-6-allylphenol. Among these phenolic compounds, 2,6-dimethylphenol, 2,6-diphenylphenol, 3-methyl-6-t-butylphenol and 2,3,6-trimethylphenol are preferable.

The phenolic compound represented by the formula (1) may be copolymerized with a polyhydric aromatic compound such as, for example, bisphenol A, tetrabromobisphenol A, resorcinol, hydroquinone and novolak resin to prepare a copolymer. In the present invention, the copolymer is also contained in the polyphenylene ether resin according to the present invention.

The oxidative coupling catalyst used for the oxidative (co) polymerization of the phenolic compound is not particularly limited, and any catalyst having a polymerization capability may be used. As a method for producing a polyphenyl ether resin by oxidative (co) polymerizing a phenol compound, for example, U.S. Patent Nos. 3306874, 3306875 and 3257357, Japanese Patent Publication (JP-B) 52-17880, Japanese Patent Application Publication (JP- A) What is disclosed in 50-51197 and 1-304119 is illustrated. All of the documents cited above are hereby incorporated by reference in their entirety.

Particular examples of the polyphenylene ether resin in the present invention are poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether), poly ( 2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-propyl-1,4-phenylene ether), poly (2,6-dipropyl-1,4-phenyl Ethylene ether), poly (2-ethyl-6-propyl-1,4-phenylene ether), poly (2,6-dibutyl-1,4-phenylene ether), poly (2,6-dipropenyl -1,4-phenylene ether), poly (2,6-dilauryl-1,4-phenylene ether), poly (2,6-diphenyl-1,4-phenylene ether), poly (2, 6-dimethoxy-1,4-phenylene ether), poly (2,6-diethoxy-1,4-phenylene ether), poly (2-methoxy-6-ethoxy-1,4-phenylene Ether), poly (2-ethyl-6-stearyloxy-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2-methyl-1 , 4-phenylene ether), poly (2-ethoxy-1,4-phenylene ether), poly (3-methyl-6-t-butyl-1,4-phenylene ether), poly (2,6 Diben A copolymer of 1,4-phenylene ether), and any base material which contains a number of repeating units constituting the above-exemplified resins.

In addition, copolymers of 2-substituted phenols such as 2,6-dimethylphenol and poly-substituted phenols such as 2,3,6-trimethylphenol and 2,3,5,6-tetramethylphenol are also contemplated by In the polyphenylene ether resin according to the present invention.

Of the polyphenylene ether resins exemplified above, poly (2,6-dimethyl-1,4-phenylene ether) and copolymers of 2,3,6-trimethylphenol and 2,6-dimethylphenol are preferred.

The polyphenylene ether resin used in the present invention may be a graft copolymer obtained by grafting the (co) polymer with a styrene compound such as styrene, α-methylstyrene, p-methylstyrene, and vinyltoluene, for example. The graft copolymer is also contained in the polyphenylene ether resin according to the present invention. When such graft copolymer is a resin powder containing a large amount of resin powder having a small powder size, the graft copolymer can also be used as a material in the present invention.

As the polyphenylene ether resin used in the present invention, from the viewpoint of obtaining a resin composition having very excellent physical properties, it is preferably about 0.3 to 0.7 dl / g, more preferably about It is preferred to have an intrinsic viscosity of 0.36 to 0.65 dl / g, most preferably about 0.4 to 0.6 dl / g.

The polycarbonate resins, polyolefin resins, polyphenylene sulfide resins and acrylonitrile / butadiene / styrene copolymer resins exemplified above used in step (i) of the present invention may be prepared according to conventional manufacturing methods. . According to this conventional method, the obtained resin is a large amount of resin powder having a small powder diameter, for example, a resin powder-containing resin having a powder diameter of about 710 μm or less in an amount of 70% by weight or more based on the total weight of the resin. It often occurs. In the present invention, it is recommended to use the above resin as the resin powder containing material for step (i).

It is preferable that the resin powder-containing material used in step (i) of the present invention contains a resin powder having a powder diameter of about 710 μm or less in an amount of about 70 to 100% by weight based on the total weight of the resin.

Step (i) of the present invention is the step of compacting the resin powder-containing material, thereby obtaining a compression molded material, wherein the resin powder adheres to each other. In this step, for example, compression is performed by passing a resin powder-containing material between two rolls standing opposite to each other, thereby obtaining a compression molded material, where the resin powder adheres to each other.

In performing the compaction, it is not always necessary to heat the resin powder-containing material. Compression can typically be performed at room temperature. The compression pressure (pressing force per unit length) of the resin powder-containing material is preferably about 300 kN / m or more, more preferably 500 kN / m or more. If the compression pressure is too low, the degree of mutual adhesion of the resin powder in the resulting compression molded material may be lowered, so that it may happen that particles having advantageous particle diameters cannot be obtained in the continuous step (ii). .

Step (ii) of the present invention is the step of pulverizing the above compression molded material and thereby obtaining particles. In this step, it is recommended to obtain particles having a diameter of about 710 μm or more in an amount of about 55 to 100% by weight based on the total weight of the particles. As the grinding machine, any commercially available machine can be used. When using a device such as a roller compactor WP 160 × 60 type (trademark of Turbo Kogyoo Co., Ltd), both the compression in step (i) and the grinding in step (ii) can be carried out in one device. have.

Step (iii) of the present invention is a step of administering the above-mentioned particles and at least one other material to the melt-kneader, followed by melt-kneading them to obtain the desired resin composition. Melt-kneaders used are ZSK series melt-kneaders (manufactured by Werner & Pfizer Gmbh); TEM series melt-kneader (manufactured by Toshiba Machine Co., Ltd.); TEX series melt-kneader (manufactured by The Japan Steel Works, Ltd.); And NCM series melt-kneaders (manufactured by Kobe Steel Ltd.).

As an example of the other materials described above used in step (iii), resins are listed. Examples of the resin include polyamide resins such as 6-nylon, 6,6-nylon and 12-nylon; Styrene-based polymer resins such as polystyrene, high impact polystyrene and styrene-butadiene-styrene triblock copolymers; Olefin polymer resins such as polypropylene, high density polypropylene, propylene-ethylene copolymer, ethylene-butene-1 copolymer, ethylene-pentene copolymer, ethylene-hexene copolymer and poly-4-methylpentene-1; Olefins such as ethylene and propylene, and for example acrylic acid esters containing methyl acrylate and ethyl acrylate, for example methacrylic acid esters containing methyl methacrylate and ethyl methacrylate, vinyl acetate, styrene, acrylic Copolymer resins with vinyl monomers such as ronitrile and glycidyl (meth) acrylate; Thermosetting resins such as polyimide resin, polyamide-imide resin, phenolic resin, alkyd resin, unsaturated polyester resin and diallyl phthalate resin DAP resin); Polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyarylene esters (eg, U polymer (trademark) manufactured by Unitika Ltd.); Polyvinyl chloride resins; Polymethyl methacrylate resins; Polyvinyl acetate resins; Polyvinyl pyridine resins; Polyvinyl carbazole resins; Polyacrylamide resins; Polyacrylonitrile resins; Polycarbonate resins; Polyphenylene sulfide resins; Polyacetal resins; Silicone resins; Polysulfone resins; Polyether sulfone resins; And fluorine-containing resins. Among these resins, when using a polyphenylene ether resin in step (i), a polyamide resin, an olefinic polymer resin or a styrene polymer resin is preferably used. When using the polycarbonate resin in step (i), polybutylene terephthalate resin is preferably used because the obtained resin composition has a wide range of uses. In view of smoothly transferring the aforementioned resin into the melt-kneader, the resin used in step (iii) is preferably a resin having a particle diameter of about 710 μm or more in an amount of about 50% by weight or more based on the total weight of the resin It contains particles.

As for the general ratio between the resin used in step (i) and the other resin used in step (iii), the former resin is about 5 to 80 parts by weight, preferably based on the weight of the two resins in total. In an amount of about 10 to 60 parts by weight, the latter resin is used in an amount of about 20 to 95 parts by weight, preferably 40 to 90 parts by weight.

Melt-kneading conditions are not particularly limited. The above conditions can be appropriately selected to melt the resin used and to obtain a resin composition having good uniformity and less degradability. The melt-kneading temperature in step (iii) can be determined according to the maximum glass transition temperature Tg or melting point Tm of the resin used. It is preferred to select the melt-kneading temperature in the range of from about 20 ° C. to about 350 ° C. above the maximum glass transition temperature Tg. The melt-kneading atmosphere is not particularly limited and may be an inert atmosphere such as air or nitrogen.

In step (iii) the melt-kneading conditions are given descriptively as follows, wherein the resin used in step (i) is a polyphenylene ether resin and the resin used in step (iii) is a polyamide resin.

As for the ratio between the polyphenylene ether resin used in step (i) and the polyamide resin used in step (iii), the polyphenylene ether resin is generally about 5 based on the total weight of the two resins. To 80 parts by weight, preferably about 10 to 60 parts by weight, more preferably 20 to 50 parts by weight; The polyamide resin is used in an amount of about 20 to 95 parts by weight, preferably about 40 to 90 parts by weight, more preferably about 50 to 80 parts by weight. If there is too much polyphenylene ether resin used, the obtained resin composition tends to impair its mechanical properties or its moldability. If the polyphenylene ether resin used is too small, the obtained resin composition tends to impair its heat resistance. The melt-kneading temperature is usually about 220 to 300 ° C, preferably about 250 to 300 ° C, more preferably about 270 to 290 ° C.

If desired, the resin used in step (i) or the resin used in step (iii) may be, for example, a dye; Pigments; Additives such as antistatic agents, antioxidants and weatherproof agents; Reinforcing agents such as inorganic fillers; And in combination with a functional-female filler such as carbon.

According to the present invention, a resin powder-containing material containing a large amount of a resin powder having a small powder diameter is treated through the steps (i) and (ii) as described above to obtain particles; The particles obtained and at least one other material are melt-kneaded in step (iii) as described above; The desired resin composition can thereby be obtained with extremely high productivity by a smooth melt-kneading operation.

Example

The invention is explained in more detail with reference to the following examples, which are given for illustration only without limiting the scope of the invention. The diameters of the powders and particles were measured according to JIS Z8801.

Example 1

Poly (2,6-dimethyl-1,) having a powder having an intrinsic viscosity of 0.408 dl / g and a powder diameter of 710 μm or less in an chloroform solvent in an amount of 80% by weight based on the total weight of the resin 4-phenylene ether) is compressed at a dosage rate of 80 kg / h at 690 kN / m and room temperature, thereby compressing the powders to one another with a length of 300 to 500 mm, a width of 70 mm and a thickness of 2 mm. Obtain the material (step (i)). The compression molded material is ground, whereby particles are obtained having a particle diameter of at least 710 μm in an amount of 52 wt% based on the total weight of the particles (step (ii)). Compression and grinding were carried out as one apparatus, roller compactor WP 160 × 60 type (trademark of Turbo Kogyoo Co., Ltd).

The obtained particles were administered from the first barrel of the melt-kneader described above at a dose rate of 195 kg / hr; And nylon 6 (other material) was administered from barrel 6 of the melt-kneader at a dose rate of 176 kg / hr (about 90% of the dose rate of the particles); And both were melt-kneaded there (step (iii)).

The dough operation was completed smoothly to obtain the desired resin composition, and the production capacity of the resin composition was found to be 371 kg / hr. The term "production volume" means the production dose obtained when the dose of resin is at its maximum.

As the melt-kneader, one-way twin screw kneader TEM-100A (trademark of Toshiba Machine Co., Ltd.) was used. The machine described above has a barrel between the screw length and the screw diameter of 38.3 and has 12 barrels, the materials being administered from barrel 1 and barrel 6 respectively.

As for the barrel temperature, the temperature of barrel 1 was set to 40 ° C., the temperature of barrel 2 was set to 190 ° C., and the temperatures of barrels 3 to 5 were set to 280 ° C., respectively, and 6 The temperatures of barrels 12 to 12 were set at 220 ° C, respectively. The rotation speed of the screw was set to 300 rpm.

Comparative Example 1

Example 1 was repeated except that step (i) and step (ii) were omitted. The poly (2,6-dimethyl-1,4-phenylene ether) could not be smoothly transferred into the kneader, so the maximum dose of resin from barrel 1 was 116 kg / hr and nylon 6 was 104 kg / hr was administered from barrel 6 at a rate of hr (about 90% of poly (2,6-dimethyl-1,4-phenylene ether)), both melt-kneaded therein. The production capacity of the resin composition was found to be 220 kg / hr, which was about 59% of Example 1.

According to the method of the present invention, even when preparing a resin composition using a material containing a large amount of a resin powder having a small powder diameter as a starting material, it is possible to perform melt-kneading operation smoothly and to provide very good productivity. Can be.

Claims (8)

Method for producing a resin composition consisting of the following steps: (i) compacting the resin powder containing material, thereby obtaining a compression molded material in which the resin powder is adhered to each other, (ii) milling the compression molded material to obtain particles, and (iii) administering said particles and one or more other materials to a melt-kneading machine and melt-kneading them to obtain a resin composition. The method of claim 1, wherein the resin powder-containing material in step (i) contains a powder diameter of 710 μm or less in an amount of about 70 to 100 wt% based on the total weight of the resin. The method of claim 1, wherein the particles in step (ii) contain a particle diameter of at least 710 μm in an amount of about 50 to 100 wt% based on the total weight of the resin. The method of claim 1, wherein the compression in step (i) is performed under a pressure of at least 300 kN / m. The method of claim 1, wherein the resin in step (i) contains a polyphenylene ether resin and the other material in step (iii) contains a polyamide resin. The method of claim 1, wherein the resin in step (i) contains a polyphenylene ether resin and the other material in step (iii) contains an olefinic polymer resin. The method of claim 1, wherein the resin in step (i) contains a polyphenylene ether resin and the other material in step (iii) contains a styrene-based polymer resin. The method of claim 1, wherein the resin in step (i) contains a polycarbonate resin and the other material in step (iii) contains a polybutylene terephthalate resin.