JP2001206995A - Polypropylene-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polypropylene-based resin composition capable of continuously exhibiting excellent antistatic ability for a long period, excellent in heat resistance and chemical resistance and useful for production of various molded products needed for the antistatic measures besides a medical peripheral member. SOLUTION: This polypropylene-based resin composition comprises 35-91 wt.% of polypropylene-based resin, 4-15 wt.% of antistatic resin and 5-50 wt.% of inorganic filler having an anisotropic shape.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polypropylene resin composition, and more particularly to a polypropylene resin composition having excellent antistatic properties for a long period of time.

[0002]

2. Description of the Related Art Conventionally, trays and containers as medical peripheral members used for conveying and sterilizing medical instruments have a surface specific resistance value of 1.
Antistatic performance of 0 × 10 ¹⁴ ohms or less is required.
A styrene-based long-lasting antistatic material such as a composite material in which an antistatic resin (such as polyetheresteramide) is blended with a BS resin is used. However, steam sterilization requires heat resistance (130 ° C. or more as a load deflection temperature), and chemical sterilization requires chemical resistance. Therefore, ABS-based materials with poor performance are limited in use. . On the other hand, attempts have been made to blend the antistatic resin with a polyolefin resin, and a resin modified with maleic anhydride or the like is interposed in order to add compatibility. However, such a method leads to denaturation of the antistatic resin, so that if sufficient compatibility is to be ensured, the antistatic performance is sacrificed. The composition is not known.

[0003]

Therefore, the present inventor has demonstrated that an excellent antistatic performance can be continuously exhibited for a long period of time.
Intensive research has been conducted to develop a polypropylene resin composition having excellent heat resistance and chemical resistance and useful for manufacturing various molded articles requiring antistatic measures, including medical peripheral members.

[0004]

As a result, the present inventor has:
By blending an inorganic filler with a composite resin consisting of a polypropylene resin and an antistatic resin, it has been found that stabilization by the filler of the composite resin exhibits excellent antistatic performance over a long period of time, and can achieve the above-mentioned problems. Was. The present invention has been completed based on such findings. That is, the present invention provides a polypropylene resin composition comprising 35 to 90% by weight of a polypropylene resin, 5 to 15% by weight of an antistatic resin, and 5 to 50% by weight of an inorganic filler having an anisotropic shape. is there.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The polypropylene resin composition of the present invention comprises a polypropylene resin, an antistatic resin and an inorganic filler as described above. Here, the polypropylene resin is not particularly limited, and various resins can be used. For example, a homopolymer or copolymer of polypropylene (block copolymer or random copolymer) or a homopolymer or copolymer of polypropylene as a main component is used. It is also possible to use polystyrene and / or a mixture of one or more rubber elastic bodies. Examples of the rubber elastic body include a styrene-butadiene copolymer elastomer, a styrene-butadiene-styrene copolymer elastomer, a styrene-isoprene block copolymer elastomer, a styrene-isoprene-styrene copolymer elastomer, and a part or all of a butadiene part. Based on styrene-based elastomers such as styrene-isoprene-styrene block copolymer elastomers, and α-olefin copolymers such as ethylene, propylene, 1-butene, 1-hexene and 1-octene. Elastomers, ethylene-α-olefin-based elastomers obtained using metallocene-based catalysts, natural rubber, polybutadiene, polysulfide rubber, thiochol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydride Phosphorus rubber,
Examples include polyester / ester rubber. Among them, 100 parts by weight of polyethylene, polyethylene,
A polypropylene-based resin obtained by combining 5 to 15 parts by weight of one or more selected from ethylene-propylene-based elastomers and ethylene-α-olefin-based elastomers obtained with a metallocene catalyst is preferred. If the amount of the rubber elastic material is less than 5 parts by weight, good impact characteristics cannot be obtained. If the amount exceeds 15 parts by weight, the impact characteristics are improved but the heat resistance is lowered. Is not preferred.

The polypropylene resin composition of the present invention comprises:
Further, it contains an antistatic resin. Here, as the antistatic resin, there is no particular limitation, various types can be used,
Either one that exhibits conductivity due to ionic conductivity or one that exhibits conductivity due to the properties of the charge transfer complex can be used. Specific examples of the ion conductive resin include (a) an organic polymer material which is fibrous or forms a fiber and is insoluble in a polypropylene resin;
(B) having a block for forming a complex or solvating a salt of an inorganic or low molecular weight organic protonic acid, which is a component (c) described later, and having good compatibility with the component (a); Mixtures of ionically conductive polymers or copolymers and (c) salts of inorganic or low molecular weight organic protic acids complexed or solvated in the polymer or copolymer of component (b) above. The organic polymer material which forms the fibrous or fibrous component (a) and is insoluble in the polypropylene-based resin may be in the form of already drawn fiber or in the form of cut staple fiber, and may have a planar network structure. , Woven pattern, non-woven fabric, felt, etc. The organic polymer material which forms a fibrous or fiber and is insoluble in the polypropylene resin is preferably a synthetic polymer fiber. Suitable fibrous or fiber-forming organic polymer materials include, for example, polyamides, copolyamides, polyesters, polyvinyl acetates, polyvinyl alcohols, modified celluloses, polyacrylates,
Examples include polymethacrylic acid ester, polyacrylonitrile, modacrylic (copolymer of acrylonitrile and vinyl chloride), polyesteramide, polyphenylene sulfide, polyfluorohydrocarbon, polyurethane, polyurea and the like. These fibers are generally from 0.01 to 2
00 mm, preferably having a length of 0.1-20 mm,
Various fiber thicknesses can be selected. The fiber thickness is usually in the range of 0.5 to 500 dtex, preferably 1 to 100 dtex
Is selected in the range. Examples of the ion-conductive polymer or copolymer as the component (b) include oligoethoxylated acrylates or methacrylates, styrenes having aromatic rings oligoethoxylated, polyether urethane, polyether urea, polyether amide, polyether ester amide, Examples thereof include a polyether ester, and the copolymer may be a random copolymer or a block copolymer, and a block copolymer is particularly preferable. Polyether amides and polyether ester amides are particularly preferred, especially block-type polyether ester amides, wherein the polyether segment comprises polyether glycol units having a molecular weight Mn of 200 to 6000 daltons, Polyamide segment having a molecular weight Mn of 200 to 6000 daltons
And polyamide (x) or polyamide (x, y)
[Here, x and y each indicate a number of 4 to 14. ]
Are preferred. Examples of the salt of the inorganic or low molecular weight organic protonic acid as the component (c) include alkali metal salts, alkaline earth metals, zinc salts and ammonium salts. Examples of the low molecular weight organic protonic acid include acids having 1 to 4 carbon atoms, such as acetic acid, trifluoroacetic acid, and the like.
Methanesulfonic acid, trifluoromethanesulfonic acid and the like can be mentioned. Particularly preferred are inorganic salts such as Li
ClO ₄ , LiCF ₃ SO ₃ , NaClO ₄ , LiBF ₄ , KBF _4, NaCF ₃ SO ₃ , KC
lO ₄ , KPF ₆ , KCF ₃ SO ₃ , KC ₄ F ₉ SO ₃ , Ca (ClO ₄ ) ₂ , Ca (PF ₆ ) ₂ ,
Mg (ClO ₄ ) ₂ , Mg (CF ₃ SO ₃ ) ₂ , Zn (ClO ₄ ) ₂ , Zn (PF ₆ ) ₂ , Ca (C
F ₃ SO ₃ ) _{2 and the} like, and these salts can produce various hydrated forms, and can be used with or without water of hydration. These salt (c) components are (b)
It is preferably used in the range of 0.05 to 10% by weight, more preferably in the range of 0.5 to 5% by weight, based on the components. The mass ratio of the component (a) to the component (b) is preferably from 20: 1 to 1:10, and more preferably 10: 1.
More preferably, it is で 1: 3.

The charge transfer complex is, for example, composed of an electron donor and an electron acceptor, formed by at least one kind of finely soluble polymer electron donor and at least one kind of polymer soluble electron acceptor, or It is preferably formed by one kind of slightly soluble polymer electron acceptor and at least one kind of polymer soluble electron donor. Examples of the electron donor include 5,6,11,12-tetrathiotetracene, 5,6,11,12-tetraselenotetracene, 2-fluoro- and 2,3-difluoro-
5,6,11,12-tetraselenotetracene, 2,
3,8,9-tetramethyl-5,6,11,12-tetrathiotetracene, 2,3,8,9-tetramethyl-
5,6,11,12-tetraselenotetracene, 2-methyl-5,6,11,12-tetrathiotetracene,
2,3,8,9-tetrafluoro-5,6,11,12
-Tetrathiotetracene, 2,3,8,9-tetrafluoro-5,6,11,12-tetraselenotetracene,
2,3-dichloro-5,6,11,12-tetraselenotetracene, 2-fluoro-5,6,11,12-tetrafluorotetracene, 2,3,6,7-tetrathiophenyl-1,4 , 5,8-Tetrathionaphthalene, 2,
3,6,7-tetramethoxyphenyl-1,4,5,8
-Tetrathionaphthalene, 2,3,6,7-tetra-4
-Pyridylthio-1,4,5,8-tetrathionaphthalene, 2,3,6,7-tetraphenylthio-1,4
5,8-tetraselenonaphthalene and the like can be mentioned.

The electron acceptor is not particularly limited as long as it is a halogen-containing organic compound capable of dissociating a halogen atom and capable of forming a charge transfer complex with an electron donor. Bromoform, trichlorobromomethane, hexachloropropane, hexachloropropene, hexachlorocyclopropane, hexachlorocyclopentadiene, hexachloroethane, octachloropropane, n-octachlorobutane, n-decachlorobutane, tetrabromoethane, hexabromoethane, tetrabromobenzoquinone, 2,4,4,6-tetrabromo-2,5-cyclohexadienone, hexabromobenzene, chloranil, hexachloroacetone, 1,
4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, 1,2,5,6,9,10-
Hexabromocyclododecane, tetrachloroethylene,
Perchlorocyclopentadiene, perchlorobutadiene, dichloroacetaldehyde-diethylacetal,
1,4-dichloro-2-butene, 1,3-dichloro-2
-Butene, 3,4-dichloro-1-butene, tetratochlorochloropropane, 1,3-dichloroacetone, 2,
3,5,6-hexachloro-p-xylene, 1,4-bis (trichloromethyl) bezen, 1,3-bromopropane, 1,6-dibromohexane, ethyl 3-chloropropionate, 3-chlorotoluene, Methyl 2-chloropropionate, 2-chloroacrylonitrile, ethyl trichloroacetate, 1,2,3-trichloropropane, 1,1,2-trichloroethane, butyl chloroformate, trichloroethylene, 2,3-
Dichloromaleic anhydride, 1,10-bromodecane,
1,12-dibromododecane, α, α′-dibromo-p
-Or -m-xylene, α, α'-dichloro-o-
Or -p-xylene, phenacyl chloride or bromide, iodoacetonitrile, 2,3-dichloro-5,6
-Dicyanobenzoquinone, 2,3-dichloropropionic acid methyl ester, 1-bromo-2-chloroethane, 1
-Bromo-2-chloropropane, chloroformic acid-2-bromoethyl ester, iodoacetic acid ethyl ester, N-chloro-, N-bromo- or N-iodosuccinimide, N-chloro-, N-bromo- or N-iodo-
Examples include phthalimide or a mixture of these compounds. Further, the above-mentioned halogen-containing compound is a thermoplastic halogen-containing polymer containing an aliphatic or cycloaliphatic side chain group, wherein the side chain group has a group of —O—, —O—CO—, —CO
-OA-OCO- (wherein A is a group having 2 to 1 carbon atoms optionally substituted by a hydroxyl group, a halogen atom or a phenyl group)
2, an alkylene group having 4 to 12 carbon atoms, a cycloalkylene group having 4 to 12 carbon atoms, a cycloalkylene-CH ₂ -group having 4 to 12 carbon atoms,
Cycloalkylene of 4 to 12 carbon atoms - (CH _{2) 2} -, shows a benzylene group or a xylylene group), or -CO-O-
And a halogen-containing polymer having at least one halogen atom at the α-, β-, γ- or ω-position. Further, the electron acceptor may be CuCl ₂ and CuBr ₂ and their hydrated, solvated or ammonium complexes.

Further, polyethylene glycol, polypropylene glycol and the like can be added to the above-mentioned antistatic resin for modification and used. Further, inorganic salts of metal components such as alkali metals and alkaline earth metals can be used. Organic salts may be added.

[0010] The polypropylene resin composition of the present invention comprises:
Further, it contains an inorganic filler having an anisotropic shape. As the inorganic filler having an anisotropic shape, generally, various inorganic fillers can be used as long as they do not have a symmetrical shape in terms of form, left and right or up and down. For example, talc, calcium carbonate, Gypsum, wollastonite, clay,
Examples thereof include glass flake, basic magnesium sulfate, potassium titanate, rock wool, glass fiber, and mica. Particularly preferred are talc, calcium carbonate, wollastonite, basic magnesium sulfate, glass fiber and mica. One or two or more of them can be used in combination. Further, to the inorganic filler having such an anisotropic shape, an inorganic or organic filler having an isotropic shape such as calcium carbonate, glass beads, glass balloon, wood flour, barium sulfate, and zinc oxide is added. You can also.

The polypropylene resin composition of the present invention comprises:
35 to 91% by weight of the polypropylene resin as described above,
It comprises 4 to 15% by weight of an antistatic resin and 5 to 50% by weight of an inorganic filler having an anisotropic shape. The antistatic resin is 4
It is blended at a ratio of 15% by weight, but is preferably in a range of 7７13% by weight. If the amount of the antistatic resin is less than 4% by weight, good antistatic performance cannot be obtained, and if it is more than 15% by weight, good heat resistance may not be obtained. The compounding amount of the inorganic filler having an anisotropic shape is 5 to 50% by weight.
It is preferably 40% by weight, more preferably 7 to 30% by weight. If the amount of the inorganic filler in the anisotropic shape is less than 5% by weight, the dispersibility of the antistatic resin becomes insufficient, and
Good heat resistance cannot be obtained, and if it is more than 50% by weight, the molding material becomes considerably brittle, and the impact resistance may be particularly insufficient. The polypropylene-based resin composition of the present invention may contain a flame retardant, a flame retardant auxiliary, an antioxidant, a weathering agent, a metal deactivator, a lubricant, etc., as needed, within a range not to impair the object of the present invention. Can be added.

[0012]

Next, the present invention will be described in more detail based on examples, but the present invention is not limited by these examples.

Examples 1-4 and Comparative Examples 1-2 Polypropylene (trade name J-, manufactured by Idemitsu Petrochemical Co., Ltd.)
3000 GP, homopolypropylene with a melt index of 30), antistatic resin B (manufactured by Sanyo Chemical Industries, Ltd.)
Compound name Pelestad 6321) and an inorganic filler (talc) having an anisotropic shape were compounded in the compounding ratio shown in Table 1, and a single screw extruder (trade name NAKATANI MACHINERY CO., LTD., N
VC-50), and the resulting pellets are injected into an injection molding machine (Nissei Plastic Industry Co., Ltd., trade name FE).
-120S), molding temperature 210 ° C., mold temperature 50
Injection molding was performed at ℃ to form a test piece. The surface resistivity, load deflection temperature and Izod impact strength of the obtained molded article were measured by the following methods, and the results are shown in Table 1. The surface resistance was measured at an applied voltage of 1000 V using a DSM8103 digital insulation meter manufactured by Toa Denpa Kogyo KK and an SME-8331 electrode shielding box. Load deflection temperature (HDT)
Was measured at 4.5 Pa using a fully automatic load deflection temperature tester manufactured by Toyo Seiki Seisaku-sho. Izod impact strength is measured by an Izod impact tester manufactured by Toyo Seiki Seisakusho (capacity: 30 kg
-Cm) (according to ASTM D256).

[0014]

[Table 1]

Examples 5 to 8 and Comparative Examples 3 to 6 Polypropylene (trade name J-manufactured by Idemitsu Petrochemical Co., Ltd.)
Table 2 shows 3000 GP, a homopolypropylene having a melt index of 30; an antistatic resin A (manufactured by Ciba Specialty Chemicals, trade name: Irgastat P-22); and an inorganic filler (talc) having an anisotropic shape. The mixture was blended at the mixing ratio, and melt-kneaded using a single screw extruder (trade name, NVC-50, manufactured by Nakatani Machinery Co., Ltd.). Molding temperature 210 using FE-120S)
Injection molding was performed at 50 ° C. and a mold temperature of 50 ° C. to form test pieces. Surface resistivity and load deflection temperature (H
DT) and Izod impact strength were measured by the above method,
The results are shown in Table 2. Further, a solvent test was performed by wiping an injection-molded plate 80 mm × 80 mm × 3.2 mm (thickness) with absorbent cotton impregnated with toluene, and visually observing the molten state of the surface of the molded product.
It is shown in the table. The ABS used in Comparative Example 5 was ABS350 manufactured by Techno Polymer.

[0016]

[Table 2]

Examples 9 to 11 and Comparative Examples 7 to 9 Polypropylene (trade name J-manufactured by Idemitsu Petrochemical Co., Ltd.)
784HP, block polypropylene with a melt index of 12), antistatic resin A (Ciba Specialty Co., Ltd.)
Chemicals, trade name Ilgasstat P-22), antistatic resin B (Sanyo Chemical Co., Ltd., Pelestat 632)
1), an elastomer A (manufactured by Dupont Dow Elastomer Co., ethylene octene copolymer) and an inorganic filler (talc) having an anisotropic shape are blended in a blending ratio shown in Table 3, and a coaxial twin screw extruder ( PCM-4, made by Ikegai Corporation
The resulting pellets are melt-kneaded using 5), and the obtained pellets are injected into an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., trade name: FE-120).
Using S), injection molding was performed at a molding temperature of 210 ° C. and a mold temperature of 50 ° C. to form test pieces. The surface resistivity, load deflection temperature (HDT) and Izod impact strength of the obtained molded article were measured in the same manner as in Example 1, and the results are shown in Table 3.

[0018]

[Table 3]

[0019]

The polypropylene resin composition of the present invention exhibits high antistatic properties for a long period of time, and is excellent in heat deformation resistance, chemical resistance and coloring properties. , Medical peripheral parts that can be sterilized using various sterilization methods such as chemical sterilization, such as trays and containers, can be provided.
It can be expected to make a great contribution to hospital infection control. In addition, the polypropylene resin composition of the present invention is not only applied to medical peripheral members, but also makes use of its antistatic performance to make use of packaging materials for electronic components such as IC trays and carrier tapes, electric appliances,
The present invention can be used for various applications requiring a so-called static electricity countermeasure such as prevention of adhesion of dirt and protection of an electronic circuit, such as a game machine, a computer, and an automobile part in which an electronic circuit is incorporated.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) (C08K 13/04 (C08K 13/04 3:34 3:34 3:26 3:26 3:30 3: 30 7:14) 7:14) F-term (reference) 4J002 AB013 AC012 AC032 AC082 BB052 BB121 BB141 BB152 BB172 BD123 BE023 BF023 BG042 BG103 BP012 BP021 CF033 CH042 CK013 CK022 CK023 CL003 CL083 CN010DG03 003 DL006 FA016 FA043 FA046 FD016 GB01

Claims (5)

[Claims] 1. A polypropylene resin composition comprising 35 to 91% by weight of a polypropylene resin, 4 to 15% by weight of an antistatic resin and 5 to 50% by weight of an inorganic filler having an anisotropic shape. 2. The polypropylene-based resin composition according to claim 1, wherein the polypropylene-based resin is a homopolymer or copolymer of polypropylene, or a polypropylene-based resin containing polystyrene and / or one or more rubber elastic bodies. object. 3. The polypropylene resin composition according to claim 1, wherein the antistatic resin is an ion conductive resin and / or a charge transfer complex. 4. An inorganic filler comprising talc, calcium carbonate,
The polypropylene resin composition according to any one of claims 1 to 3, which is one or more selected from wollastonite, glass fiber, basic magnesium sulfate, and mica. 5. The method according to claim 1, wherein the surface resistivity is 1.0 × 10 ¹⁴ ohm or less and the load deflection temperature is 130 ° C. or more.
5. The polypropylene resin composition according to any one of 4.