JPH1088005A - Organic thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To homogeneously disperse a cured silicone powder to thereby obtain an organic thermoplastic resin composition having a low tendency to be statically charged by blending an organic thermoplastic resin with a cured silicone powder containing a surfactant. SOLUTION: This resin composition at least consists of an organic thermoplastic resin and a cured silicone powder which contains at least 0.5wt.% surfactant. The surfactant preferably comprises a nonionic surfactant in particular. The content of the cured silicone powder may be usually the same as that of the conventional cured silicone powders used in thermoplastic resins. For example, it is preferably 0.01-40wt.%. If the content is below this range, the characteristics, such as lubricity and blocking resistance, cannot be sufficiently imparted to the obtained resin composition. If the content is above the range, the processability and mechanical characteristics of the resin composition obtained will be deteriorated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic organic resin composition comprising at least a thermoplastic organic resin and a cured silicone powder. More specifically, the present invention relates to a thermoplastic organic resin in which the powder is uniformly finely dispersed and has a small chargeability. Composition.

[0002]

2. Description of the Related Art By blending a cured silicone powder with a thermoplastic organic resin such as a polyethylene resin, a polypropylene resin, an acrylic resin, a polycarbonate resin, and a polystyrene resin, it is possible to impart properties such as lubricity and blocking resistance to the resin. Are known. Examples of the thermoplastic organic resin composition comprising at least such a thermoplastic organic resin and a cured silicone powder include a thermoplastic organic resin composition comprising a thermoplastic organic resin, a polymethylsilsesquioxane powder, and graphite (Japanese Patent Laid-Open No. 50-151
No. 949), a thermoplastic organic resin composition comprising a thermoplastic organic resin and polymethylsilsesquioxane powder (see JP-A-54-57551), and a thermoplastic resin comprising a thermoplastic organic resin and a silicone rubber powder. Organic resin composition (see JP-A-60-127367)
Is exemplified.

However, these thermoplastic organic resin compositions do not uniformly and finely disperse the cured silicone powder, and therefore have a problem that they do not sufficiently exhibit properties such as lubricity and blocking properties. there were. Further, generally, an antistatic agent such as a surfactant is blended to reduce the chargeability of the thermoplastic organic resin, but when the cured silicone powder is blended with this, the chargeability does not decrease, There was a problem that dust easily adhered.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have intensively studied the above-mentioned problems, and as a result, have reached the present invention. That is, an object of the present invention is to provide a thermoplastic organic resin composition in which a cured silicone powder is uniformly finely dispersed and has small chargeability.

[0005]

The present invention provides a thermoplastic organic resin composition comprising at least a thermoplastic organic resin and a cured silicone powder, wherein the powder contains at least 0.5% by weight of a surfactant. It is characterized by being.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present composition, a thermoplastic organic resin is a main component, and its properties are not limited, and it may be an elastomer at room temperature. As the thermoplastic organic resin, ethylene, propylene, 1-butene, 1-
Polyethylene resins, low-density polyethylene resins, high-density polyethylenes, ultra-high-molecular-weight polyethylene resins, polypropylene resins consisting of homopolymers or copolymers of α-olefins such as pentene, 1-hexene and 4-methyl-1-pentene; Polyolefin resins such as ethylene- (meth) acrylate copolymer resins comprising copolymers of α-olefins with monomers other than α-olefins such as vinyl acetate, methyl methacrylate and maleic acid; acrylic acid; Methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, (meth) ) Benzyl acrylate, 2-hydroxy (meth) acrylate Chill, glycidyl (meth) acrylate, (meth) (meth) acrylic acid esters such as diethylaminoethyl acrylate, ethyl ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate,
Homopolymers or copolymers of acrylic monomers such as polyfunctional (meth) acrylates such as neopentyl glycol di (meth) acrylate, and the amount of these acrylic monomers and styrene monomer such as styrene and α-methylstyrene Body, vinyl acetate, vinyl chloride, ethylene monomers such as vinylidene chloride, phenylmaleimide, cyclohexylmaleimide,
Acrylic resin such as copolymer with maleimide monomer such as anhydrous maleimide; polyvinyl chloride resin, polystyrene resin, high impact polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile- Acrylic rubber
Styrene copolymer resin, acrylonitrile-ethylene propylene rubber-styrene copolymer resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polyamide resin such as nylon, polyacetal resin, polycarbonate resin, modified polyphenylene ether resin , Polyvinyl acetate resin, polysulfone resin, polyether sulfone resin, polyphenylene sulfide resin, polyarylate resin, polyamideimide resin, polyetherimide resin, polyetheretherketone resin, polyimide resin, liquid crystal polyester resin, polytetrafluoroethylene resin , Styrene, olefin, ester, urethane, amide, fluorine, vinyl chloride, etc. Mer resins, and mixtures and copolymers of two or more of these thermoplastic organic resins are exemplified, preferably a polyolefin resin, an acrylic resin.

In the present composition, the cured silicone powder comprises:
It is a component for imparting properties such as lubricity and anti-blocking properties to the present composition, and is characterized by containing at least 0.5% by weight of a surfactant, and preferably has a content of 0.5 to 0.5% by weight. 20% by weight, more preferably 1-2.
0% by weight, particularly preferably 3 to 20% by weight. This is because, when a cured silicone powder having a surfactant content less than this range is blended with a thermoplastic organic resin, it tends to be difficult to uniformly and finely disperse the same or to reduce the chargeability. Because
The upper limit of the surfactant content is not defined, but a cured silicone powder exceeding this range tends to have poor mechanical strength.

Examples of the surfactant include polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenol, polyoxyalkylene alkyl ester, polyoxyalkylene sorbitan ester, polyethylene glycol, polypropylene glycol, and ethylene oxide such as diethylene glycol trimethylnonanol. Nonionic surfactants such as adducts; anionic surfactants such as hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, myristylbenzenesulfonic acid, and sodium salts thereof. Activator; octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide,
Hexadecyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, dioctadecyldimethylammonium hydroxide, tallow trimethylammonium hydroxide, cationic surfactants such as coconut oil trimethylammonium hydroxide,
Mixtures of two or more of these surfactants are exemplified, and nonionic surfactants are particularly preferred.

As a method for determining the content of the surfactant in the cured silicone powder, this powder is dispersed in an organic solvent such as isopropanol, and then the dispersion is filtered through filter paper, and the organic solvent is removed from the filtrate. It can be determined from the weight of the surfactant obtained by removal.

Generally, the particle size of the cured silicone powder may be the same as that of a conventional cured silicone powder used for a thermoplastic organic resin. For example, the average particle size is 0.1 to 200 μm. It is particularly preferable that the thickness be 0.1 to 100 μm. Also,
Examples of the shape of the cured silicone powder include a spherical shape and an irregular shape, and a spherical shape is particularly preferable. The properties of the cured silicone powder include gel,
Rubber-like and hard resin-like are exemplified, and in particular, rubber-like is preferable.

The method of preparing the cured silicone powder includes, for example, pulverizing a cured silicone, curing a curable silicone composition into a powder, or curing the composition in a dispersed state in water. Method of impregnating a surfactant into the cured silicone powder obtained by the method, a method of curing a curable silicone composition containing a surfactant into a powder, and dispersing the curable silicone composition in an aqueous solution of a surfactant. After curing in a state, a method of removing water can be mentioned. In particular, a method of curing a curable silicone composition in an aqueous solution of a surfactant in a dispersed state and then removing water is preferable. Examples of the curing mechanism of the curable silicone composition include an addition reaction curing type, a condensation reaction curing type, and a radical reaction curing type using an organic peroxide, and in particular, an addition reaction curing type and a condensation reaction curing type. preferable.

In the present composition, the content of the cured silicone powder may be generally the same as that of a conventional cured silicone powder used for a thermoplastic organic resin, for example, 0.01 to 40% by weight. It is preferable that the content is more preferably 0.1 to 10% by weight, and particularly preferably 0.2 to 5% by weight. This is because if the content of the cured silicone powder is less than this range, the resulting thermoplastic organic resin composition tends to be unable to sufficiently impart properties such as lubricity and anti-blocking properties. If the content exceeds this range, the processability and mechanical properties of the obtained thermoplastic organic resin composition tend to decrease.

In the present composition, as long as the object of the present invention is not impaired, other optional components such as an inorganic filler, oleamide, erucamide, stearamide, stearic monoglyceride, stearic triglyceride, Compounding organic compounds such as hydroishi fatty acid amine, amino fatty acid sodium salt, betaine compound, N, N-bishydroxydiethylalkylamine, lubricant, antistatic agent, antioxidant, antibacterial agent, heat stabilizer, and ultraviolet absorber. Can be.

The method for preparing the present composition is not limited. For example, a thermoplastic organic resin, a cured silicone powder, and other optional components are preliminarily mixed by a mixing device such as a Henschel mixer, and then mixed with a kneader mixer. Examples thereof include a method of melting and mixing with a kneading device such as a Banbury mixer, a single-screw continuous kneader, and a twin-screw continuous kneader, and a method of melting and mixing these components with the above-described kneading device.

The present composition can be formed into various shapes, for example, into a sheet or a film. When a film is formed from this composition, the composition can be melted and formed into a sheet, and then the sheet can be monoaxially or biaxially stretched to form a film. The thickness of this film is preferably in the range of 0.1 μm to 1 mm, particularly preferably in the range of 0.5 to 200 μm.
This film may be a single layer or a multilayer such as two layers or three layers. Further, the surface of the film can be subjected to plasma treatment or metal deposition.

[0016]

EXAMPLES The thermoplastic organic resin composition of the present invention will be described in more detail with reference to examples. In addition, the viscosity in an Example is a value measured at 25 degreeC. The properties of the cured silicone powder and the properties of the thermoplastic organic resin composition were measured by the following methods. [Average Particle Diameter of Cured Silicone Powder] The (number) average particle diameter of the cured silicone powder was determined by an image processing apparatus linked to an optical microscope with a magnification of 1500 times. [Content of Surfactant in Cured Silicone Powder] A dispersion is prepared by adding 1000 g of isopropanol to 100 g of the cured silicone powder, and the dispersion is stirred with a stirrer, for example,
Using a homodisper at 1000 rpm for 10 minutes,
After further stirring at 500 rpm for 10 minutes, this was left at room temperature for 12 hours. Thereafter, the dispersion was filtered through filter paper to collect a filtrate. Then, 750 g of isopropanol was added to the cured silicone powder remaining on the filter paper to prepare a dispersion, and the dispersion was stirred at 1000 rpm for 10 minutes using a homodisper. This dispersion was filtered through filter paper to collect a filtrate. This filtrate was combined with the filtrate collected earlier, and the evaporator was used at 70 ° C. at 70 ° C.
Isopropanol was distilled off under the condition of mmHg. The weight of the obtained surfactant was measured. The surfactant was analyzed by proton nuclear magnetic resonance spectroscopy, gel permeation chromatography, and infrared spectroscopy to identify this component. [Dispersibility of cured silicone powder in thermoplastic organic resin]
The dispersibility (kneading property) when melt-kneading the cured silicone powder into the thermoplastic organic resin is defined as follows. The dispersibility is somewhat poor,
Δ: When this powder was very hard to bite, the dispersibility was poor, and X was shown. [Chargeability of Thermoplastic Organic Resin Composition] A method of attaching the carbon toner to the thermoplastic organic resin composition was visually observed by a dirt chamber test. That is, the capacity 1
A molded article (film, sheet) of the thermoplastic organic resin composition was suspended in a 20-liter closed container, 1.5 g of carbon toner for a copying machine was charged, and the toner was circulated at a wind speed of 10 m / sec for 1 minute. Thereafter, the molded article is taken out, the appearance is observed, and the case where a small amount or a small amount of toner is uniformly adhered is regarded as having low chargeability. , Δ; When the toner was unevenly attached and a flower pattern was present, the chargeability was large, and indicated as ×; [Haze of Film] The haze of two films was measured according to the method specified in ASTM D1003. [Blocking Resistance of Film] The overlapping area of the films was set to 1 cm × 1 cm, and a weight of 1 kgf was applied thereto and left for 1 day. Thereafter, the film was subjected to a peel test, and the maximum peel strength (kgf / cm ² ) was measured.

REFERENCE EXAMPLE 1 100 parts by weight of a condensation-curable silicone rubber composition having a viscosity of 45 centistokes was mixed with polyoxyethylene nonyl phenyl ether (H
LB = 13.1) The mixture passed through a homogenizer while being mixed with an aqueous solution (about 5 ° C.) of 6 parts by weight and 120 parts by weight of pure water was further mixed with 240 parts by weight of pure water to obtain a silicone rubber composition. An emulsion was prepared. This emulsion was allowed to stand at room temperature for one day to cure the silicone rubber composition to obtain an aqueous dispersion of silicone rubber powder. Thereafter, water was removed by spraying the aqueous dispersion in hot air at 300 ° C. to obtain spherical silicone rubber powder (A). The properties of this silicone rubber powder (A) are shown in Table 1.

REFERENCE EXAMPLE 2 100 parts by weight of an addition-curable silicone rubber composition having a viscosity of 430 centistokes was mixed with 11 parts by weight of polyoxyethylene nonylphenyl ether (HLB = 13.1) and 120 parts by weight of pure water. The mixture passed through a homogenizer while being mixed with an aqueous solution (about 5 ° C.) was further mixed with 240 parts by weight of pure water to prepare an emulsion of a silicone rubber composition. This emulsion was allowed to stand at room temperature for one day to cure the silicone rubber composition to obtain an aqueous dispersion of silicone rubber powder. Thereafter, water was removed by spraying the aqueous dispersion in hot air at 300 ° C. to obtain spherical silicone rubber powder (B). Table 1 shows the properties of the silicone rubber powder (B).

Reference Example 3 An aqueous dispersion of silicone rubber powder prepared in the same manner as in Reference Example 1 was filtered through a filter paper, and the filtered silicone rubber powder was washed with an aqueous ethanol solution and pure water. Thereafter, the silicone rubber powder was dried in a hot air circulating oven at 100 ° C. to obtain a spherical silicone rubber powder (C). Table 1 shows the characteristics of the silicone rubber powder (C).

REFERENCE EXAMPLE 4 The addition reaction-curable silicone rubber composition used in Reference Example 2 was cured while being sprayed in hot air at 300 ° C. to obtain a spherical silicone rubber powder (D). The properties of this silicone rubber powder (D) are shown in Table 1.

[0021]

[Table 1]

Examples 1 and 2, Comparative Examples 1 to 3 100 parts by weight of a polypropylene resin (Sumitomo Noblen FK145 manufactured by Sumitomo Chemical Co., Ltd.), silicone rubber powders A, B and C having the properties shown in Table 1 , And D, 2 parts by weight, 2,6-di-t-butyl-p-cresol 0.1 part by weight, and calcium stearate 0.01 part by weight were uniformly mixed with a Henschel mixer.
The resulting mixture was melt-kneaded at ℃ to prepare a polypropylene resin composition. While this polypropylene resin composition is being injection molded at 220 ° C.,
The film was biaxially stretched at 0 ° C. to form a film having a thickness of 20 μm. For comparison, a film was prepared in the same manner using a polypropylene resin composition prepared in the same manner as described above except that the silicone rubber powder was not blended. The properties of these films are shown in Table 2.

[0023]

[Table 2]

Examples 3 and 4, Comparative Examples 4 and 6 Methacrylic resin (Acrypet VH manufactured by Mitsubishi Rayon Co., Ltd.)
100 parts by weight, a silicone rubber powder A shown in Table 1,
2.0 parts by weight of each of B, C, and D, and 3.0 parts by weight of an alkylsulfonic acid-based antistatic agent were uniformly mixed with a Henschel mixer, and then melt-mixed at 250 ° C. to obtain an acrylic resin composition. Prepared. This acrylic resin composition was extruded at 250 ° C. to form a 2 mm sheet. Also, for comparison, a sheet was prepared in the same manner as described above for an acrylic resin composition prepared in the same manner as described above except that the silicone rubber powder was not blended.
The properties of these sheets are shown in Table 3.

[0025]

[Table 3]

[0026]

The thermoplastic organic resin composition of the present invention comprises at least a thermoplastic organic resin and a cured silicone powder, wherein the powder contains at least 0.5% by weight of a surfactant. Therefore, there is a characteristic that this powder can be finely dispersed uniformly and the chargeability of the composition can be reduced.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Haruhiko Furukawa 2-2 Chikusa Beach, Ichihara-shi, Chiba Dow Corning Silicone Co., Ltd.

Claims (5)

[Claims] 1. A thermoplastic organic resin composition comprising at least a thermoplastic organic resin and a cured silicone powder, wherein the powder contains at least 0.5% by weight of a surfactant. Composition. 2. The thermoplastic organic resin composition according to claim 1, wherein the surfactant is a nonionic surfactant. 3. The thermoplastic organic resin composition according to claim 1, wherein the cured silicone powder is a silicone rubber powder. 4. The cured silicone powder is obtained by curing a curable silicone composition in a dispersed state in an aqueous solution of a surfactant, and then removing water. 2. The thermoplastic organic resin composition according to 1. 5. The thermoplastic organic resin composition according to claim 1, wherein the content of the cured silicone powder in the thermoplastic organic resin composition is 0.01 to 40% by weight.