JP2001048992A - Holding master batch composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a master batch composition comprising a large amount of a filler capable of uniformly dispersing a natural resin. SOLUTION: This molding master batch composition comprises 0.1-10 pts.wt. of a stabilizer as a fatty acid metal salt, etc., and 0.1-10 pts.wt. of an antistatic agent based on 100 pts.wt. of 15-85 wt.% of a thermoplastic resin composed of powder and granule and 15-85 wt.% of a filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a masterbatch composition for resin molding, particularly a masterbatch composition suitable for injection molding, extrusion molding and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, colored resin pellets have been used for coloring molded articles. In other words, colored pellets according to the color of the final molded product are supplied to the molding machine, and it is necessary to prepare materials of each color in advance according to the consumption amount, so that the stock amount of the pellets for production swells. There is a problem that the cost increases.

[0003] One type of resin for molding, for example, a natural (non-colored) resin, and a masterbatch mixed with this resin at a predetermined ratio and diluted with the resin to a predetermined color density are used. Since the above problem relating to the stock amount is solved, in the field of coloring, a method utilizing a masterbatch has become widespread.

For example, Japanese Patent Application Laid-Open No. Hei 8-291222 discloses a technique concerning a coloring master batch.

[0005] By the way, resins are mixed with various additives for modification. For example, inorganic fillers such as glass fiber and talc are added to improve strength and scratch resistance. Depending on the purpose of use of the resin, the type and amount of the additive differ.

[0006]

Therefore, a resin (natural resin) pellet containing no additive and a master batch pellet mixed with the additive contain a high concentration of additive, and the master batch is diluted with the resin. Thus, it is considered that obtaining a resin containing additives of a predetermined type and a compounding ratio is effective in solving the above-mentioned problems concerning stock. However, the content of the additive is usually about several percent to about 30%. Therefore, when the amount added to the base resin of the master batch is, for example, three-fold diluted, it may reach nearly 90% (% by weight, the same applies hereinafter). When additives are blended in such a ratio, problems such as classification, dispersion, and distribution occur, and the additives cannot be uniformly dispersed in the resin. Therefore, it is necessary to stock many types of resin pellets corresponding to the types of products, and there has been a problem that production efficiency cannot be improved. In addition, when the compounding ratio of the additive is reduced, the dilution ratio is reduced, and the substantial effect of using the master batch is lost.

According to the present invention, when a natural resin (a resin containing no inorganic filler) is mixed so as to have a predetermined blending amount as a molding resin, the masterbatch contains a large amount of filler. It is an object of the present invention to provide a molding masterbatch composition that can be uniformly and stably dispersed.

[0008]

In order to solve the above-mentioned problems, the present inventors have studied the problems at the time of forming the above-mentioned master batch, that is, the causes of dispersion, classification, and distribution.
As a result, one of the causes that the high-concentration filler mixed into the base resin of the masterbatch is not uniformly formed in the resin forming the final product is an agglomeration (primary agglomeration) of the fillers and this primary agglomerate. To form agglomerates (secondary agglomerates) in which a plurality of particles form larger additive particles,
Another reason for the non-uniform dispersion in the kneading device of the molding machine is that the master batch pellets are electrically aggregated in the mixed resin pellets (natural resin) in the hopper of the molding machine and classified. To determine the point of
The present inventors have determined that the masterbatch pellets are difficult to be smoothly diluted into resin (natural) pellets due to the high concentration of the additives, and have led to the present invention.

That is, the present invention provides (1) a masterbatch composition for molding to be mixed with resin pellets, wherein the thermoplastic resin (A) is 15 to 85% by weight and the filler (B) is 15 to 85% by weight. (A) + (B)
Relative to 100 parts by weight of fatty acid, fatty acid metal salt, fatty acid ester, polyester wax, polyethylene wax, fatty acid amide, higher alcohol fatty acid ester, or polyhydric alcohol fatty acid amide or stabilizing agent (C). 0.1 to 10 parts by weight of a combination of quaternary ammonium salt, polyether type, polyesteramide type, polyhydric alcohol fatty acid ester type, monoglycerin fatty acid ester, and ethylene oxide as antistatic agent (D) Any one of these or a combination of two or more of them
A master batch composition for molding, characterized by comprising 0 parts by weight and the above (A) to (D), (2) prepared so that the bulk specific gravity of the master batch substantially matches the bulk specific gravity of the resin pellets. A masterbatch composition for molding according to (1), wherein the masterbatch composition for molding is mixed with resin pellets, wherein the first thermoplastic resin (A1) is a granular material. 10 to 80% by weight and the second
5 to 75% by weight of powder as the thermoplastic resin (A2), and 15% as the resin composition (A) composed of A1 and A2.
~ 85% by weight, and 15-85% by weight as the filler (B)
And fatty acids, fatty acid metal salts, fatty acid esters, polyester waxes, polyethylene waxes, fatty acid amides, higher alcohol fatty acid esters, polyhydric esters as stabilizing aids (C) with respect to 100 parts by weight of the above (A) + (B). 0.1 to 10 parts by weight of one or a combination of a plurality of alcohol fatty acid amides, and a quaternary ammonium salt, a polyether-based, a polyesteramide-based, or a polyhydric alcohol fatty acid ester as an antistatic agent (D) System, monoglycerin fatty acid ester, ethylene oxide adduct, or a combination of two or more of these, 0.1 to 10 parts by weight, and the above (A) to (D)
And a method for producing a masterbatch composition for molding, characterized by dynamically kneading the composition.

[0010] The masterbatch composition of the present invention uses a thermoplastic resin in combination with a powder and a fluid as described below, and the components (C) and (D) are important. The occurrence of the above-mentioned problems that hinder the realization of stable uniform dispersion can be prevented, and the master batch pellets and the resin pellets can be uniformly mixed and smoothly melted.

The masterbatch composition of the present invention is preferably prepared so that the bulk specific gravity of the masterbatch substantially matches the bulk specific gravity of the resin pellets to be blended. In this case, since the mixed and dispersed master batch pellets can be prevented from being classified by gravity in the resin pellets (natural resin), the uniformity of the mixing is further improved in combination with the action of the antistatic agent (D). it can.

In the method for producing a masterbatch composition for molding to be mixed with resin pellets of the present invention, it is important that the thermoplastic resin is made into granules and powder, and these are blended with a specific composition.

That is, 10 to 80% of the particles of the first thermoplastic resin (A1) and the powder 5 of the second thermoplastic resin (A2)
% To 75%, 15 to 85% as a resin composition (A) containing a component containing (A1) + (A2) or more, and 15% to 85% as a filler (B), and (A) + ( 0.1 to 10 parts by weight of a fatty acid, a fatty acid metal salt, a fatty acid ester, a polyester wax, a polyethylene wax, a fatty acid amide, a higher alcohol fatty acid ester, or a polyhydric alcohol as a stabilizer (C) with respect to 100 parts by weight of B) Any one of fatty acid amides or a combination thereof, and the antistatic agent (D) may be the above-mentioned Δ (A) +
(B) 0.1 to 10 parts by weight of quaternary ammonium salt, polyether type, polyester amide type, polyhydric alcohol fatty acid ester type, monoglycerin fatty acid ester, ethylene oxide adduct per 100 parts by weight By dynamically melting and kneading one or a combination of one or more of these, a masterbatch pellet that contains a filler at a high concentration and can be mixed with a natural resin etc. to uniformly disperse the filler is stably obtained. Can be manufactured.

The thermoplastic resin (A) is not particularly limited, but is preferably one of polypropylene, polyethylene, ethylene-propylene copolymer, polystyrene, ABS, polycarbonate, and polyamide, or a composite of these. The first and second thermoplastic resins A
1, A2 is the same as thermoplastic resin A, but A1 and A2
May be different types of resins. These resins are
Those which are compatible with the resin selected as the resin pellet (natural resin) are preferable, and the same resin material as the natural resin is particularly preferable.

In the present invention, the combined use of granules and powder makes it possible to relatively easily produce a masterbatch composition containing a large amount of filler. 5% to 75 powder
%, Preferably 5% to 30%, and the remaining 80% to 10%.
%, Or 80% to 55% of granules for a suitable amount of powder. The powder forms a very good admixture with the finely divided filler. This is simultaneously mixed with the resin forming granules in the kneading apparatus. Therefore, in the case of resin particles alone, at first, the filler only adheres to the surface of the particles, and it takes time for the particles to be uniformly dispersed throughout, and during that time, static electricity is generated because the resin is rubbed in the molten state Although the uniformity of the filler is hindered, the effect of adding the stabilizer (C) and the antistatic agent (D) in addition to the combination of the powder and the granules is extremely short. Therefore, the amount of induced static electricity can be significantly reduced.

In the present invention, as the granules, ordinary commercial pellets can be used as they are. For example, major axis 2-6
mm. The powder is obtained by pulverizing the pellets into 0.05
One having a particle size of about 1.0 mm is used. Preferably 0.1-0.8 mm, more preferably 0.1-0.5
It is almost spherical in the range of mm. The pulverization can be performed by cooling the pellets with liquid nitrogen or the like and cutting the pellets at a high speed (impact) with a pulverizer.

As the filler (B), inorganic fillers such as talc, glass fiber, whisker, barium sulfate,
Silica, calcium carbonate, wollastonite, titanium white, aluminum hydroxide, magnesium hydroxide, and the like, and organic fillers, for example, various types of fiber waste such as wood powder, leather powder, and cotton can be used. These mixtures ｛(A)
+ (B)} indicates that the components are in a complementary relationship. Filler (B)
Is 15 to 85%. Therefore, the remaining 85 to 15%
Is a resin composition (A). Filler (B) is limited to 85%. The filler (B) is preferably made to have a high content in order to increase the dilution ratio of the master batch, but if the resin composition (A) does not exceed a certain amount, granulation becomes difficult. The easier the granulation, the better the resin composition (A). Therefore, the filler (B) content is up to 85%, preferably up to 80%, more preferably 70%. As the lower limit, a realistic value of 15% or more may be selected from the purpose of the master batch itself.

The mixture {(A) + (B)} is defined as 100 parts by weight based on the following.

The stabilizing aid (C) has a function of preventing the filler (B) from agglomerating in the masterbatch pellets. Fatty acids, fatty acid metal salts, fatty acid esters, polyester waxes, polyethylene waxes, fatty acid amides, 0.1 to higher alcohol fatty acid ester, polyhydric alcohol fatty acid ester, polyhydric alcohol fatty acid amide
10 parts by weight, preferably 0.5 to 3.0 parts by weight. If the amount is less than 0.1 part by weight, the dispersing effect is not sufficient. If the amount exceeds 10 parts by weight, physical properties may be affected, and a bleeding phenomenon may be observed. Fatty acids include, for example, stearic acid, oleic acid and palmitic acid, with stearic acid being particularly preferred. Examples of the fatty acid metal salt include calcium stearate, magnesium stearate, aluminum stearate, lithium stearate, barium stearate, zinc stearate, and calcium palmitate. Of these, calcium stearate and magnesium stearate are preferable. Examples of the fatty acid ester include diamond wax (manufactured by Shin Nippon Science Co., Ltd.), interstub (manufactured by Nippon Interstab Co., Ltd.), and Hoechst wax (manufactured by Hoechst Japan Co., Ltd.).
Examples of polyester wax and polyethylene wax include, for example, sun wax (manufactured by Sanyo Chemical Industries, Ltd.).
Examples of the fatty acid amide include methyl bissteroamide and ethylene bissteroamide, with ethylene bissteroamide being particularly preferred. Examples of higher fatty acid esters include stearic acid monoglyceride, oleic acid monoglyceride, stearyl stearate, and cetyl palmitate.

The antistatic agent (D) contains the above-mentioned Δ (A) +
(B) 0.1 to 10 parts by weight, preferably 0.2 to 0.3 parts by weight, per 100 parts by weight.

As the means for dynamically melting and kneading, those commonly used for kneading resins, for example, a multi-screw extruder such as a single-screw or twin-screw, a kneader, a Banbury mixer and the like can be used.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION <Examples> (Table of Components) (A) Thermoplastic synthetic resin A1. Ethylene-propylene copolymer (K7730, manufactured by Chisso Corporation) 22 kg A2. Ethylene-propylene copolymer powder (K7730 powder, manufactured by Chisso Corporation) 22 kg (B) Inorganic filler B1. Talc powder (average particle size: 3 to 4 μm) 56 kg (C) Stabilizing aid C1. Zinc stearate 300 g (D) Antistatic agent D1. 500 g of electrostripper TS-5 (manufactured by Kao Corporation) (kneading step) A1 uses commercially available pellets, and A2 can be obtained by low-temperature pulverization of the commercially available pellets. Although A2 has the same mixing ratio as A1, A2 requires a pulverizing step. Therefore, from the viewpoint of cost, A1 is preferably set to be larger than the above ratio.

The above A to D are placed in a super mixer (300 liters, manufactured by Kawada Seisakusho), mixed at 1760 rpm for 5 minutes, and a twin screw extruder (PCM80 / 4, manufactured by Ikegai Iron Works).
The mixture was melt-mixed in 2) and a master batch pellet was produced by a cold cut method.

The master batch pellets are made to substantially correspond to the pellet specific gravity of the polypropylene resin pellets (natural resin) to be mixed at the time of injection molding. That is, due to the cut shape of the strand of the masterbatch to be pelletized, the unevenness of the cross-sectional shape of the ejection of the extrusion die, and the like, even a masterbatch having a large specific gravity reduces the bulk specific gravity and obtains a bulk specific gravity close to a natural resin.

The resulting masterbatch pellets have a talc content of 56% (% by weight). This master batch pellet 1 was mixed with polypropylene resin pellets (natural resin) 3 at a ratio of 3 and mixed with a tumble mixer for 15 minutes, fed to an in-line screw type plasticizer of an injection molding machine, and subjected to ordinary injection molding. A flat plate (sample plate) was formed.

Sample plate: 150 × 150 × 3
(Mm) flat plate Injection molding machine: 140 tons (IS-140B, manufactured by Toshiba Machine Co., Ltd.) (Method of evaluating molded products) (1) Uniformity of dispersion 1) Measurement of molded products (samples) in a steady molding cycle Measure the weight.

2) The talc content of a sample piece cut from a sample arbitrarily extracted according to a time series in a steady molding cycle is measured.

3) The presence or absence of talc powder aggregation on the surface of the molded product is visually inspected.

4) In addition, the presence or absence of color unevenness and gloss unevenness of the external appearance is visually inspected.

(Evaluation of sample plate) 1: 100 shots, average 68.4 g, maximum 69.
4 g, minimum value 66.8 g 2: talc content averaged 15.8%, maximum value 16.7
%, Minimum value 15.6% 3: No aggregation of talc powder observed 4: Uneven color and gloss unevenness Not observed Reference Example Same ethylene propylene copolymer as in Example (K773
0, manufactured by Chisso Corporation) and melt-kneaded with an extruder to pelletize the same talc as in the example so that the content was 16%.

In the same manner as in the example, a sample plate was manufactured by injection molding.

(Evaluation) 1: 100 shots, average 69.2 g, maximum 70.
0g, minimum value 68.7g 2: talc content average 16.1%, maximum value 16.2
%, Minimum value 16.0% 3: talc powder agglomeration not recognized 4: color unevenness, gloss unevenness not recognized From the results of the above Examples and Reference Examples, filling prepared via the master batch composition of the present invention. It is understood that the agent-containing molding resin composition has the same uniform dispersibility as the filler-containing molding resin composition kneaded and prepared without using the master batch method.

<Comparative Example 1> A masterbatch pellet was produced in the same manner as in Example except that components C and D were omitted, and a sample plate was similarly obtained.

(Evaluation) 1: 100 shots, average 70.4 g, maximum value 74.
1 g, minimum 63.9 g 2: talc content average 16.2%, maximum 26.6
%, Minimum value: 5.4% 3: Aggregation of talc powder Many agglomerates of 10 to 50 μ are observed 4: Uneven color and gloss unevenness are observed Many results are clearly inferior to the examples.

<Comparative Example 2> Ingredient A of Example 1 was changed to A1 only.
Granulation was carried out under the same conditions as in the example except that the mixture was the same as in the example except that the weight was 4 kg, and kneaded with a super mixer for 10 minutes (twice the time of the example). In the obtained masterbatch, variation in the amount of talc was clearly recognized from the appearance of each grain.

Comparative Example 3 Component A was 10% and Component B was 9
Granulation was performed in the same manner as in Example except that the amount was 0% by weight. A small amount of the component B powder that was not kneaded into the pellets was observed, and the formed pellets were also brittle, so that the outer shape was collapsed in the tumble mixer and the uniformity of dispersion was lost.

[0037]

According to the present invention, a high-quality masterbatch composition containing a large amount of filler uniformly dispersed therein can be realized. Compared to the case of preparing many kinds of pellets kneaded with fillers, if you prepare a large amount of resin that does not contain inorganic fillers such as a small amount of masterbatch pellets and several times natural resin compared to this Since the amount of processing of the resin containing the inorganic filler can be reduced to a fraction while maintaining the same quality as the conventional method, the cost of the resin material is reduced, and the manufacturing cost of the molded product is reduced. be able to.

Natural resins and the like can also be used for applications that do not require inorganic fillers, or several kinds of inorganic fillers having different compounding ratios can be appropriately set in a molding machine. The effect is that the number of types of resin pellets can be greatly reduced, thereby reducing management costs.

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Claims (3)

[Claims] 1. A masterbatch composition for molding mixed with resin pellets, comprising 15 to 85% by weight as a thermoplastic resin (A) and 15 to 85% by weight as a filler (B). A) + 100% by weight of (B), as fatty acid, fatty acid metal salt, fatty acid ester, polyester wax, polyethylene wax, fatty acid amide, higher alcohol fatty acid ester, polyhydric alcohol fatty acid amide 0.1 to 10 parts by weight of any one or a combination thereof, and quaternary ammonium salt, polyether type, polyesteramide type, polyhydric alcohol fatty acid ester type, monoglycerin as antistatic agent (D) Any one of a fatty acid ester and an ethylene oxide adduct or a combination thereof. 10 parts by weight, more (A), characterized in that consisting of ~ (D), the molding masterbatch composition. 2. The molding master batch composition according to claim 1, wherein the bulk specific gravity of the master batch is adjusted to substantially match the bulk specific gravity of the resin pellet. 3. A masterbatch composition for molding mixed with resin pellets, wherein 10% to 80% by weight of granules is used as the first thermoplastic resin (A1).
5 to 75% by weight of powder as the second thermoplastic resin (A2)
And a resin composition (A) comprising A1 and A2,
5 to 85% by weight, 15 to 85% by weight as the filler (B), and 100 parts by weight of (A) + (B) above. Fatty acid, fatty acid metal salt, fatty acid as the stabilizing aid (C). 0.1 to 10 parts by weight of any one of ester, polyester wax, polyethylene wax, fatty acid amide, higher alcohol fatty acid ester, and polyhydric alcohol fatty acid amide, or a combination thereof, as antistatic agent (D) 0.1 to 10 parts by weight of a quaternary ammonium salt, a polyether type, a polyesteramide type, a polyhydric alcohol fatty acid ester type, a monoglycerin fatty acid ester, an ethylene oxide adduct, or a combination of two or more thereof. A masterbatch composition for molding, characterized by dynamically melting and kneading the above (A) to (D). The method of production.