JP2002053758A - Thermoplastic resin composition highly loaded with filler - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in molding properties and characteristics though highly loaded with a filler, and having realized excellence in dimensional stability, hardness, cost performances and the like owing to high filler loading. SOLUTION: The thermoplastic resin composition highly loaded with a filler comprises a thermoplastic resin, a filler in an amount larger than that of the thermoplastic resin and 0.1-20 pts.wt., based on 100 pts.wt. of the thermoplastic resin, of a fluorine-modified acrylic processing auxiliary.

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 a high filler content, and more particularly, to a thermoplastic resin composition having a high filler content and excellent moldability and physical properties.
In addition, the present invention relates to a thermoplastic resin composition having excellent dimensional stability, hardness, cost performance and the like realized by high filler loading.

[0002]

2. Description of the Related Art In general, the main purpose of highly filling a thermoplastic resin with various fillers is to reduce the cost of a resin molded article and to improve various physical and chemical properties, for example, to reduce the coefficient of linear expansion, to reduce the strength and the like. Various fillers are selected and used depending on the purpose, such as improvement of elastic modulus, increase of hardness, improvement of abrasion resistance, improvement of heat resistance, and the like.

[0003]

However, if the thermoplastic resin is filled with a high amount of filler, the melt tension at the time of melting decreases, and the molding itself becomes difficult due to poor cohesion of the resin and agglomeration of the filler. Naturally, the physical properties of the molded article also deteriorate. This tendency is particularly remarkable in an ABS resin or a polypropylene resin having low compatibility with the filler.

[0004] Accordingly, an object of the present invention is to provide a thermoplastic resin composition which is excellent in moldability and physical properties while being highly filled with filler, and in which excellent dimensional stability, hardness and cost performance are realized by highly filled filler. In providing things.

[0005]

According to the present invention, a thermoplastic resin, a filler in an amount greater than the same amount as the thermoplastic resin, and 0.1 to 20 parts by weight of fluorine per 100 parts by weight of the thermoplastic resin are provided. A highly filled thermoplastic resin composition characterized by comprising a modified acrylic processing aid.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Action] In the present invention, a filler is mixed with a thermoplastic resin by blending a fluorine-modified acrylic processing aid at a specific ratio to a resin composition comprising a thermoplastic resin and a filler. Even when compounded in an amount larger than the same amount, excellent moldability can be obtained, and various physical properties of the formed molded article can be significantly improved.

When the thermoplastic resin is filled with the same amount or more of the filler, the resin composition has a low melt tension, a large drawdown at the time of molding, and is inferior in moldability. Further, even if the molding is performed forcibly, the improvement of the dimensional stability and the like, which are the original objects of the filler filling, cannot be achieved, and the impact resistance is also inferior (Comparative Examples 1 to 4 described later).
reference). On the other hand, according to the present invention, when a small amount of a fluorine-modified acrylic processing aid is blended with the thermoplastic resin, even when the same amount of filler is blended with the thermoplastic resin, the draw during molding can be performed. The down can be suppressed to a small value, and the moldability of this resin composition can be significantly improved. In addition, the dimensional stability and impact resistance of the formed resin molded article can be significantly improved as compared with those without the fluorine-modified acrylic processing aid (Example 1 described later). To 6).

In the present invention, the fluorine-modified acrylic processing aid may be used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the thermoplastic resin. is important. When the amount of the processing aid is below the above range, the effects of improving moldability and improving various physical properties cannot be obtained.On the other hand, when the amount exceeds the above range, the viscosity of the resin composition becomes too high and molding is difficult. And the cost of the resin composition increases, which is not preferable.

The fluorine-modified acrylic processing aid used in the present invention has a chemical structural feature that an acrylic resin is modified with a fluoroalkyl or fluoroalkylene chain. By blending this fluorine-modified acrylic processing aid, even when the amount of resin with respect to the filler is small, the cohesion between the filler and the thermoplastic resin at the time of melt-kneading is improved, and the melt tension of this composition is increased to form the composition. It is considered that this contributes to the improvement of the performance.

In addition, the thermoplastic resin composition with a high filler content of the present invention achieves excellent dimensional stability, hardness, flame retardancy, heat resistance, heat resistance, abrasion resistance, cost performance, etc. as it is due to the high filler content. There is an advantage that it is done.

[Thermoplastic resin] As the thermoplastic resin,
For example, low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDP)
E), linear low density polyethylene (LLDPE), polypropylene (PP), poly 1-butene, poly 4-methyl-
Polyolefins such as 1-pentene or random or block copolymers of α-olefins such as ethylene, propylene, 1-butene and 4-methyl-1-pentene; ethylene-vinyl acetate copolymer, ethylene-acrylic copolymer Copolymers such as polystyrene, impact-resistant polystyrene, acrylonitrile / styrene copolymer (AS), acrylonitrile / butadiene / styrene copolymer (ABS), α-methylstyrene / styrene copolymer, etc. Styrene resin; Nylon 6, Nylon 6-6, Nylon 6-10, Nylon 1
1, polyamides such as nylon 12; polyethylene terephthalate (PET), polybutylene terephthalate (P
Thermoplastic polyester such as BT), polycarbonate,
Examples thereof include polyphenylene oxide and the like, and a mixture thereof.

An acrylonitrile-butadiene-styrene copolymer (ABS) is one of the thermoplastic resins suitable for the purpose of the present invention. ABS resin itself is a general-purpose resin excellent in various properties such as moldability, impact resistance, rigidity, tensile strength, gloss, etc., but has a problem that dispersibility of filler is low. When used in combination with a system processing aid, the dispersibility of the filler can be improved.

The ABS resin is obtained by copolymerizing PS with acrylonitrile (AN) and polybutadiene (B) for the purpose of modifying polystyrene (PS), and has an AN content of generally 20 to 40% by weight, particularly 25% by weight. And the content of polybutadiene is generally 5 to 70%.
By weight, especially those in the range of 10 to 30% by weight are readily available. AS resin has improved chemical resistance with increasing AN content, and also improved rigidity, tensile strength, load deflection temperature, surface hardness, barrier properties, light resistance, and conversely, fluidity and heat stability. Is reduced. Therefore, a material having a predetermined AN content can be selected and used according to required characteristics. The ABS resin is obtained by dispersing and reinforcing polybutadiene as a rubber component in the above-mentioned AS resin, and has further improved impact resistance, rigidity, tensile strength, and gloss. In this ABS resin, A
It has a structure in which polybutadiene particles are dispersed as a dispersion layer in a continuous phase of the S resin, and has a fine particle diameter, generally in the range of 0.1 to 0.9 μm.

[0014] ABS resin grades include gloss grade, good flow grade, extrusion grade, super heat resistant grade,
Various types such as blow grades are known, and these grades can be selectively used according to the purpose. Generally, the melt flow rate (JIS K72
(Measured at 190 ° C. under a load of 2160 g, the same applies hereinafter) in the range of 1 to 70 g / 10 min.

Another example of a thermoplastic resin that can be suitably used for the purpose of the present invention is a polypropylene resin. The polypropylene resin also has a problem that the dispersibility of the filler is low, but the dispersibility of the filler can be improved by using it in combination with the fluorine-modified acrylic processing aid.

As the polypropylene-based resin, one having an isotactic structure or one having a syndiotactic structure can be used. In addition to homopolypropylene, random copolymerized polypropylene or block copolymerized polypropylene is used. The polypropylene resin used is
Generally, the melting point is in the range of 140 to 170 ° C., and the melt flow rate (measured at a temperature of 230 ° C. under a load of 2160 g according to JIS K7210, the same applies hereinafter) is 0.5.
It is desirably in the range of ６０60 g / 10 minutes.

Various types of polypropylene resin can be selected according to the use of the foamed molded article. For example, homopolypropylene can be used for applications requiring heat resistance and rigidity, and impact resistance is required. For this purpose, random copolymerized polypropylene or block copolymerized polypropylene is used. Examples of the comonomer in these copolymers include one or a combination of two or more olefins other than propylene, for example, α-olefins such as ethylene and 1-butene.

Other thermoplastic resins suitably used for the purpose of the present invention include polyethylene resins. The density of the polyethylene resin is 0.90 to 0.9.
Those having a range of 7 g / cm ³ and a melt flow rate (JIS K7210) of 0.06 to 45 g / 10 minutes are suitable.

As the polyethylene resin, high density polyethylene (HDPE), medium density polyethylene (MDP)
E), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE) and the like are used alone or in combination of two or more.

[Filler] As the filler, various organic and inorganic fillers are used according to the purpose. These organic and inorganic fillers are all useful for the purpose of increasing the amount, improving the dimensional stability and the hardness, but especially when the purpose is to improve the heat resistance and the flame retardancy, etc. An organic filler is preferably used, and when the purpose is to improve impact resistance and texture, an organic filler is preferably used. Of course, an inorganic filler and an organic filler can be used in combination.

As the inorganic filler, colloidal silica,
Silica fillers such as anhydrous silicic acid, hydrous silicic acid, synthetic silicate, light and heavy calcium carbonate, activated calcium carbonate, kaolin, silane surface treated clay, calcined clay, alumina white, aluminum hydroxide, talc powder , Dolomite, alumina sulfate, barium sulfate, magnesium carbonate, magnesium silicate, basic magnesium silicate (talc), magnesium oxide, calcium sulfate, pumice powder, glass powder, asbestos powder, zinc oxide, titanium dioxide, carbon black, etc. is there. Further, an inorganic fine hollow body (hereinafter referred to as an inorganic balloon) can also be used. Examples of the inorganic balloon include a silicate balloon and a non-silicate balloon, and the silicate balloon includes a shirasu balloon, a pearlite, a glass balloon, a silica balloon,
Fly ash balloons and the like, non-silicate balloons,
Alumina balloons, zirconia balloons, carbon balloons and the like can be exemplified.

The organic filler has a specific gravity of 0.8.
Those composed of natural, regenerated, semi-synthetic or synthetic polymers in the range of 9 to 2.20 are preferably used. As natural organic fillers, cellulosic fillers are preferred, including softwood, hardwood, bark, wood, bamboo, grain husks, fruit husks, powders of other plants, pulp, paper, waste paper, and the like. Can be These cellulosic fillers are 1
Those having a particle size of 50 μm or less are preferred. Other examples of the organic filler include synthetic polymer powders having a particle shape such as a cubic shape, a polyhedral shape, an elliptical shape, an oval shape, a spherical shape, a cylindrical shape, a prismatic shape, and an irregular shape. Nylon 6, Nylon 6,6, Nylon 6/66 copolymer, M
Examples include polyamide resins such as XD-6, nylon 4, and nylon 610, polyester resins such as polyethylene terephthalate, ABS resins, styrene resins, acrylic resins, vinyl chloride resins, and vinylidene chloride resins. Powdered rubber can also be used. Further, an organic micro hollow body (hereinafter referred to as an organic balloon) can also be used. Examples of the organic balloon include a thermosetting resin balloon and a thermoplastic resin balloon. The thermosetting resin balloon includes a phenol resin balloon, an epoxy resin balloon, and a urea resin balloon, and the thermoplastic resin balloon includes Saran. Balloons, polystyrene balloons, polymethacrylate balloons, polyvinyl alcohol balloons, and styrene-acrylic balloons can be exemplified. Also, a balloon of a crosslinked thermoplastic resin can be used.

[Fluorine-Modified Acrylic Processing Aid] The fluorine-modified acrylic processing aid is, as already pointed out, a fluoroalkyl or a fluoroalkylene chain obtained by modifying an acrylic resin. The fluoroalkylene chain may have intervening oxygen atoms in the chain.

For modification with a fluoroalkyl or fluoroalkylene chain, a modification means by copolymerization of a fluorine monomer and an acrylic monomer can be used. Examples of the fluorine-based monomer include tetrafluoroethylene, hexafluoropropylene, vinyl fluoride, vinylidene fluoride, trifluorochloroethylene, perfluorovinylpropyl ether, perfluoroallyl butyl ether, perfluorodivinylethyl ether, and perfluorovinylallyl. Ether is exemplified.

On the other hand, acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate,
Isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth)
Examples include ester monomers such as n-amyl acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-octyl (meth) acrylate. it can. However, the above (meth) acrylic acid means acrylic acid or methacrylic acid. Of these, methyl methacrylate is preferred. Further, it may contain a monomer other than acrylic, such as styrene, α-methylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, and vinyl acetate.

Further, the fluorine-modified acrylic processing aid may contain a small amount of a functional group-containing monomer component.
It has a salt group, an amide group, a hydroxyl group, an amino group, an epoxy group, a methylol group, and an etherified methylol group, and specific examples thereof include the following. Ethylenically unsaturated carboxylic acids or anhydrides thereof; acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic anhydride, itaconic anhydride and the like. Amide group-containing monomers; (meth) acrylamide and the like. Hydroxyl group-containing monomers; vinyl alcohol, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, propylene glycol monoester acrylate and the like. Amino group-containing monomer; dimethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, vinylpyridine, 2-vinyl-5-ethylpyridine, oxazolylethyl (meth) acrylate, (meth)
Hydroxyethylaminoethyl acrylate and the like. Epoxy group-containing monomers; (meth) acrylic acid glycidyl ether, allyl glycidyl ether, butane monoxide and the like. A monomer having a methylol group and an etherified methylol group; dimethylolated (meth) acrylamide,
Etherified products thereof, for example, ethyl etherified products and butyl etherified products.

In the fluorine-modified acrylic processing aid used in the present invention, the fluorine monomer component and the acrylic monomer component exist in the form of a random copolymer, a graft copolymer, and a block copolymer. can do.

[Resin Composition] In the present invention, the filler is preferably contained in an amount of 100 to 900 parts by weight, particularly 100 to 500 parts by weight, per 100 parts by weight of the thermoplastic resin. If the compounding amount of the filler is less than the above range, it is not suitable for the purpose of the present invention of highly filling the filler, and dimensional stability, hardness, flame retardancy, heat resistance, abrasion resistance, cost performance, etc. Tend to be difficult to improve. On the other hand, if the compounding amount of the filler is larger than the above range, the moldability tends to decrease, and the material tends to be brittle, resulting in a decrease in physical properties even when the fluorine-modified acrylic processing aid is used in combination.

On the other hand, the fluorine-modified acrylic processing aid is
It is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the thermoplastic resin.
When the amount of the processing aid is below the above range, the effects of improving moldability and improving various physical properties cannot be obtained.On the other hand, when the amount exceeds the above range, the viscosity of the resin composition becomes too high and molding is difficult. And the cost of the resin composition increases, which is not preferable.

The composition of the present invention may contain other compounding agents known per se, such as a plasticizer, a colorant, a heat stabilizer, a weather stabilizer, an antioxidant, an antioxidant, a light stabilizer, and an ultraviolet absorber. At least one of an agent, an antistatic agent, a lubricant such as metal soap and wax, and a modifying resin or rubber can be blended according to a formulation known per se.

For example, by adding a plasticizer to the resin composition of the present invention, the melt kneading property of the resin composition is improved,
Workability can be improved. As the plasticizer, phthalate plasticizer, adipate plasticizer, ester plasticizer such as succinate plasticizer,
Examples include polyester-based plasticizers, phosphate-based plasticizers, and chlorine-based plasticizers, and fatty acid esters are particularly preferred. The plasticizer is preferably used in an amount of 0.1 to 50 parts by weight per 100 parts by weight of the thermoplastic resin.

The resin composition of the present invention comprises various components
If necessary, it can be prepared by dry-blending with a blender, Henschel mixer, or the like, and then supplying it to a Banbury mixer, a kneader, a roll, a single-screw extruder, a twin-screw extruder, and melt-kneading. And it can be molded into various products by a known molding method such as extrusion molding, injection molding, blow molding, compression molding, and vacuum molding.

[0033]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

The materials used in the following examples are as follows. (1) Thermoplastic resin ABS resin Melt flow rate (JIS K7210) 4 g / 10 min Polypropylene (PP) Melt flow rate (JIS K7210) 6 g / 10 min (2) Filler Wood flour Particle size 100 μm Talc Particle size 7 μm Waste paper particle size 200μm bamboo powder Particle size 1000μm (3) Fatty acid ester Melting point (mp) 90 ℃

The measurement and evaluation were performed as follows. (1) Drawdown The extrudate hangs under its own weight between the mold and the sizing. At this time, the hanging distance from the straight line of the mold and the sizing to the extrudate was x, and the evaluation was made according to the following criteria. Drawdown ○: Drawdown is small (x ≦ 1) △: Drawdown is slightly large (3>x> 1) ×: Drawdown is large (x ≧ 3) (2) Formability Evaluation was based on criteria. Moldability ：: Very good moldability △: Good moldability ×: Extrusion molding is possible, but an arbitrary shape is not obtained (3) Linear expansion Measured from dimensional change of extrudate from 0 ° C to 60 ° C. (4) Charpy impact value Measured according to JIS-K-7111.

Example 1 100 parts by weight of ABS resin
200 parts by weight of wood flour, 2 parts by weight of a fluorine-modified acrylic processing aid and 3 parts by weight of a fatty acid ester are dry-blended at room temperature for 20 minutes, supplied to an extruder, melt-kneaded, extruded from a die, and placed on a sheet. Extrusion molding was performed. Cylinder temperature is 160-210 ° C, die temperature is 200
° C and the L / D of the screw was 24. Table 1 shows the obtained results.

Example 2 Polypropylene (PP) 10
0 parts by weight, 200 parts by weight of wood flour, 2 parts by weight of a fluorine-modified acrylic processing aid, and 3 parts by weight of a fatty acid ester are dry-blended at room temperature for 20 minutes, supplied to an extruder, melt-kneaded, and cut from a die. It was extruded and extruded into a sheet-like molded body. The cylinder temperature was 160-210C, the die temperature was 180C, and the L / D of the screw was 24. Table 1 shows the obtained results.

Example 3 In Example 2, wood flour 20
Extrusion was performed in the same manner as in Example 2 except that 150 parts by weight of talc was used instead of 0 parts by weight. Table 1 shows the obtained results.

Example 4 In Example 2, wood flour 20
Extrusion was performed in the same manner as in Example 2 except that 150 parts by weight of waste paper was used instead of 0 part by weight. Table 1 shows the obtained results.

[Example 5] In Example 2, wood flour 20
Extrusion was carried out in the same manner as in Example 2 except that 150 parts by weight of bamboo powder was added instead of 0 parts by weight. Table 1 shows the obtained results.

[Embodiment 6] In the embodiment 2, the wood flour 20
In the same manner as in Example 2 except that a combination of 200 parts by weight of wood flour and 50 parts by weight of talc is blended instead of 0 parts by weight,
Extrusion was performed. Table 1 shows the obtained results.

Comparative Example 1 Example 1 was repeated except that the blending of the fluorine-modified acrylic processing aid was omitted.
Extrusion molding was performed in the same manner as described above. Table 1 shows the obtained results.
Shown in

Comparative Example 2 Example 2 was repeated except that the compounding of the fluorine-modified acrylic processing aid was omitted.
Extrusion molding was performed in the same manner as described above. Table 1 shows the obtained results.
Shown in

Comparative Example 3 The procedure of Example 5 was repeated except that the compounding of the fluorine-modified acrylic processing aid was omitted.
Extrusion molding was performed in the same manner as described above. Table 1 shows the obtained results.
Shown in

Comparative Example 4 Example 6 was repeated except that the blending of the fluorine-modified acrylic processing aid was omitted.
Extrusion molding was performed in the same manner as described above. Table 1 shows the obtained results.
Shown in

Comparative Example 5 Extrusion molding was carried out in the same manner as in Example 2 except that the blending of the wood flour was omitted. Table 1 shows the obtained results.

[0047]

[Table 1]

[0048]

According to the present invention, a thermoplastic resin, a filler in an amount greater than the same amount as the thermoplastic resin, and a fluorine-modified acrylic in an amount of 0.1 to 20 parts by weight per 100 parts by weight of the thermoplastic resin. Thermoplastic resin composition with excellent fillability, high moldability and physical properties by containing a processing aid, and excellent dimensional stability, hardness, cost performance etc. Things can be provided.

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Claims (3)

[Claims] 1. A thermoplastic resin, a filler in an amount greater than the same amount as the thermoplastic resin, and 0.1 to 20 parts by weight of a fluorine-modified acrylic processing aid per 100 parts by weight of the thermoplastic resin. A filler-filled thermoplastic resin composition characterized by comprising: 2. The composition according to claim 1, wherein the filler is a cellulosic filler and / or an inorganic filler. 3. The composition according to claim 1, wherein the thermoplastic resin is an olefin polymer or an ABS resin.