JP2010174196A - Thermoplastic resin composition and molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which is excellent in flowability, flexibility, scale stability, compression set properties, is low in stickiness, and can provide a molded product capable of being treated with a bleaching agent. <P>SOLUTION: The thermoplastic resin composition comprises 30-95 pts.mass of an amorphous propylene-1-butene copolymer (A), 5-70 pts.mass of a crystalline polypropylene resin (B), and an acid-modified polyolefin wax (C) having an acid value of 20-70 mg/g, wherein the amorphous propylene-1-butene copolymer (A) is composed of 90-97 mass% of a propylene monomer unit and 3-10 mass% of a 1-butene monomer unit; the component (A) and the component (B) are totalized to be 100 pts.mass; and the acid-modified polyolefin wax (C) has a content of 0.3-10 pts.mass relative to 100 pts.mass which is the total of the propylene-1-butene copolymer (A) and the polypropylene resin. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

 The present invention relates to a thermoplastic resin composition and a molded product used for applications of films, sheets, bottles, and sealing materials.

Crystalline polypropylene resins are inexpensive and have excellent heat resistance, and are therefore used in various applications such as household appliances, automobile parts, miscellaneous goods, films, sheets, bottles, and sealing materials. Among these applications, in the fields of films, sheets, bottles, sealing materials, etc., a crystalline (propylene-ethylene) random copolymer having a crystallinity lower than that of a crystalline propylene homopolymer has been conventionally used. It was.
However, since the low crystalline (propylene-ethylene) random copolymer has a lower melting point than the crystalline propylene homopolymer, dimensional stability and compression set may be insufficient. Therefore, a polypropylene-based resin composition in which an amorphous polypropylene resin is blended with a crystalline polypropylene resin has been proposed as one that improves flexibility and dimensional stability and compression set (patent document). 1).
However, the polypropylene resin composition has a large compression set when used for a long period of time or at a high temperature. In addition, the molded product obtained from the propylene-based resin composition tended to exhibit stickiness when stacked with other molded products.

 By the way, as a thermoplastic elastomer used for said use, a styrene-type thermoplastic elastomer (henceforth TPS), an olefin type thermoplastic elastomer (henceforth TPO), a polyester-type thermoplastic elastomer (henceforth, hereinafter). Also known as TPEE).

TPS is a block copolymer composed of a soft segment such as polybutadiene and polyisoprene and a hard segment of polystyrene, or a hydrogenated product thereof. Generally, TPS is used in combination with polypropylene in the fields of films, sheets, bottles, sealing materials and the like (see, for example, Patent Document 2). However, TPS has a problem that it has low fluidity and dimensional stability and is sticky.
TPO is composed of a soft segment such as ethylene-propylene-conjugated diene copolymer (EPDM) and a hard segment of polypropylene. In the field of films, sheets, bottles, sealing materials, etc., a dynamic crosslinking type obtained by crosslinking by melting and kneading TPO in an extruder in the presence of a crosslinking agent and a polymerization initiator (for example, peroxide). Are mainly used (see, for example, Patent Document 3). However, the molded product obtained from TPO has a problem that the stickiness when stacked with other molded products is large.
TPEE is composed of a soft segment of polyether and a hard segment of polyester (see, for example, Patent Document 4). This TPEE has a problem that when it is bleached with a bleaching agent containing hypochlorous acid as a main component, the surface is eroded and the physical properties are lowered.

JP 2003-313434 A Japanese Patent Laid-Open No. 10-298257 JP-A-8-41250 JP 2000-309893 A

As described above, conventionally, in addition to excellent fluidity, all of flexibility, dimensional stability and compression set properties are excellent, stickiness is small, and bleaching treatment mainly containing hypochlorous acid has been processed. A resin material from which a possible molded product can be obtained has not been known.
Therefore, the present invention is a molded article that is excellent in fluidity, excellent in flexibility, dimensional stability, compression set characteristics, low stickiness, and capable of processing a bleaching agent mainly composed of hypochlorous acid. It aims at providing the thermoplastic resin composition from which this is obtained. Another object of the present invention is to provide a molded article that is excellent in flexibility, dimensional stability, compression set characteristics, has low stickiness, and can be treated with a bleaching agent containing hypochlorous acid as a main component.

[1] Amorphous propylene-1-butene copolymer (A) 30 to 95 parts by mass composed of 90 to 97% by mass of propylene monomer units and 3 to 10% by mass of 1-butene monomer units And 5 to 70 parts by mass of the crystalline polypropylene resin (B) (however, the sum of the component (A) and the component (B) is 100 parts by mass), and acid modification with an acid value of 20 to 70 mg / g Containing a polyolefin wax (C),
The content of the acid-modified polyolefin wax (C) is 0.3 to 10 parts by mass with respect to 100 parts by mass in total of the propylene-1-butene copolymer (A) and the polypropylene resin. A thermoplastic resin composition.
[2] The thermoplastic resin composition according to [1], wherein the polypropylene resin (B) is a propylene homopolymer.
[3] The thermoplastic resin composition according to [1] or [2], wherein the acid-modified polyolefin wax (C) is an acid-modified polypropylene wax.
[4] A molded product obtained by molding the thermoplastic resin composition according to any one of [1] to [3].

The thermoplastic resin composition of the present invention is excellent in fluidity, excellent in flexibility, dimensional stability, compression set characteristics, low stickiness, and capable of treating a bleaching agent mainly composed of hypochlorous acid. Is possible.
In addition, the molded article of the present invention is excellent in flexibility, dimensional stability and compression set characteristics, has low stickiness, and can be treated with a bleaching agent containing hypochlorous acid as a main component.

(Thermoplastic resin composition)
The thermoplastic resin composition of the present invention contains an amorphous propylene-1-butene copolymer (A), a crystalline polypropylene resin (B), and an acid-modified polyolefin wax (C) as essential components. .

<Propylene-1-butene copolymer (A)>
The propylene-1-butene copolymer (A) is a copolymer composed of a propylene monomer unit and a 1-butene monomer unit.
The propylene-1-butene copolymer (A) is an amorphous copolymer. Here, the term “amorphous” means that a crystal melting peak and a crystallization peak are not observed by a differential scanning calorimeter (hereinafter referred to as DSC).

  The content of the 1-butene monomer unit in the propylene-1-butene copolymer (A) is 3 to 10% by mass, preferably 3 to 7% by mass (provided that the propylene-1-butene copolymer ( The total amount of A) is 100% by mass). If the content of the 1-butene monomer unit in the propylene-1-butene copolymer (A) is 3% by mass or more, the compression set characteristic tends to be good, and if it is 10% by mass or less. Similarly, compression set characteristics tend to be good.

The propylene-1-butene copolymer (A) is produced by a liquid phase polymerization method such as suspension polymerization or solution polymerization, a gas phase polymerization method, or the like.
The polymerization temperature, polymerization pressure, and polymerization temperature are appropriately selected. For example, the polymerization temperature is selected from −20 ° C. to 100 ° C., the polymerization pressure is selected from normal pressure to 6 MPa, and the polymerization time is selected from the range of 30 minutes to 20 hours.
Specifically, a propylene-1-butene copolymer produced by the method described in JP-A-11-193309 is preferable.

<Crystalline polypropylene resin (B)>
The crystalline polypropylene resin (B) is a propylene homopolymer, a copolymer of propylene and a monomer other than propylene, and is other than the propylene-1-butene copolymer (A).
Specific examples include propylene homopolymers such as isotactic polypropylene or syndiotactic polypropylene, random copolymers of propylene and a small amount of ethylene, block copolymers of propylene and a small amount of ethylene, and the like. . Among these, a propylene homopolymer is preferable because compression set characteristics are further improved.

The melting point of the crystalline polypropylene resin (B) is preferably 120 to 176 ° C. If the melting point of the crystalline polypropylene resin (B) is 120 ° C. or higher, sufficient heat resistance is obtained,
If it is 176 degrees C or less, the melt-kneading with an extruder and the shaping | molding process with a molding machine can be performed easily.
The crystallinity of the crystalline polypropylene resin (B) is preferably 30 to 85% by mass. If the crystallinity of the crystalline polypropylene resin (B) is 30% by mass or more, the heat resistance tends to be good, and if it is 85% by mass or less, the dimensional stability tends to be good.

Examples of the method for producing the crystalline polypropylene resin (B) include a production method using a Ziegler-Natta type catalyst in which a titanium-containing solid transition metal component and an organic metal component are combined.
The transition metal component used in the Ziegler-Natta type catalyst includes titanium, magnesium and halogen as essential components, and a solid component having an electron donating compound as an optional component, or titanium trichloride. As the organometallic component, An aluminum compound is mentioned.

Examples of the polymerization method for producing the crystalline polypropylene resin (B) include a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, or a multistage polymerization method combining these. In these polymerization methods, when obtaining a propylene homopolymer, only propylene is polymerized, and when obtaining a copolymer, monomers other than propylene and propylene are polymerized.
In addition, as a crystalline polypropylene resin (B), you may use a commercially available thing.

<Acid-modified polyolefin wax (C)>
The acid-modified polyolefin wax (C) is a modified product obtained by chemically bonding a carboxylic acid or a carboxylic anhydride to a homopolymer or copolymer of ethylene or propylene, such as an acid-modified polyethylene wax or an acid-modified polypropylene. A wax is mentioned. Examples of the carboxylic acid include (meth) acrylic acid, and examples of the carboxylic acid anhydride include maleic anhydride.
Among the acid-modified polyolefin waxes (C), acid-modified polypropylene wax is preferable because the stickiness of a molded product obtained from the thermoplastic resin composition can be further reduced.

  The acid value of the acid-modified polyolefin wax (C) is 20 to 70 mg / g, preferably 33 to 55 mg / g. The acid value here is the number of mg of potassium hydroxide required to neutralize 1 g of the acid-modified polyolefin specified by JIS K 0070. Even if the acid value of the acid-modified polyolefin wax (C) is less than 20 mg / g or more than 70 mg / g, the stickiness of the molded product tends to increase.

The acid-modified polyolefin wax (C) preferably has a melt viscosity of 80 to 1500 mPa · s. The melt viscosity here is a value measured at 140 ° C. in accordance with ASTM D-3236 using a Brookfield thermocell viscometer.
If the melt viscosity of the acid-modified polyolefin wax (C) is 80 mPa · s or more, the stickiness of the molded product tends to be small, and if it is 1500 mPa · s or less, the fluidity tends to be better.

  The content of the acid-modified polyolefin wax (C) is 0.3 to 10 parts by mass with respect to 100 parts by mass of the total amount of the propylene-1-butene copolymer (A) and the crystalline polypropylene resin (B). The amount is preferably 1 to 6 parts by mass. Even if the content of the acid-modified polyolefin wax (C) is less than 0.3 parts by mass or more than 10% by mass, the stickiness of a molded product obtained from the thermoplastic resin composition tends to increase. Become.

<Combination>
In the thermoplastic resin composition of the present invention, the propylene-1-butene copolymer (A) is 30 to 95 parts by mass and the crystalline polypropylene resin (B) is 5 to 70 parts by mass, preferably propylene-1 -Butene copolymer (A) is 65-85 mass parts, and crystalline polypropylene resin (B) is 15-35 mass parts. However, the sum total of (A) component and (B) component is 100 mass parts. Even if the propylene-1-butene copolymer (A) is less than 30 parts by mass or more than 95 parts by mass, the compression set characteristics of the molded product tend to be low.

<Other ingredients>
If necessary, the thermoplastic resin composition of the present invention comprises amide wax, rubber process oil, acid-unmodified polyethylene wax, crystal nucleating agent, clearing agent, heat stabilizer, ultraviolet stabilizer, ultraviolet absorber, ozone degradation. Antistatic agents, weathering stabilizers, foaming agents, antifogging agents, rust prevention agents, ion trapping agents, flame retardants, flame retardant aids, inorganic fillers, anti-aging agents and light stabilizers; Various additives such as additives, slip agents, internal release agents, colorants, dispersants, anti-blocking agents, lubricants, antibacterial agents, petroleum resins, foaming agents, foaming aids, high-frequency processing aids, organic pigments, inorganic pigments, dyes, etc. An agent may be contained.

<Manufacturing method>
The thermoplastic resin composition of the present invention is obtained by blending and mixing the above components (A) to (C) and other components.
Examples of the mixing method at that time include a method of mixing using a Henschel mixer, a V-type blender, a ribbon blender, a tumbler blender, or the like. Moreover, after the mixing, it can be melt kneaded with a single screw extruder, a twin screw extruder, a kneader, a Banbury mixer, etc., and further granulated or pulverized.

(Molding)
The molded article of the present invention is obtained by molding the thermoplastic resin composition.
Examples of molding methods include injection molding, compression molding, injection compression molding, T-die film molding, stretched film molding, inflation film molding, sheet molding, calendar molding, pressure molding, vacuum molding. Method, pipe molding method, profile extrusion molding method, hollow molding method, injection hollow molding method, injection stretch hollow molding method, blow molding method, laminate molding method and the like.
By these molding methods, a film-shaped (or sheet-shaped) or three-dimensional molded product is obtained.

The molded product of the present invention includes, for example, automobile parts, bicycle parts, electric / electronic equipment parts, wire covering materials, building materials, agricultural / fishery / horticultural supplies, chemical industrial supplies, civil engineering materials, industrial / industrial materials, furniture, stationery, etc. It can be used for daily and miscellaneous goods, containers and packaging, toys and leisure goods.
Examples of automobile parts include hoses, tubes, gaskets, packing, weather strips, various seal sponges, washer liquid drain tubes, and fuel tank cushion materials.
Examples of bicycle parts include a bicycle belt, a handle grip, and a saddle.
Examples of the electric / electronic device parts include home appliance members, refrigerator supplies, lighting fixtures, various electric covers, and the like.
Examples of the electric wire include a plastic cable, an insulated electric wire, and an electric wire protective material.
Building materials include, for example, walls and ceiling materials such as ribs, baseboards, panels and tarpaulins; roof materials such as corrugated sheets, fences and roofing materials; floor materials such as sill materials and tiles, joints and joints Waterproofing applications such as sticks and waterproof sheets; equipment and equipment parts such as ducts, cable ducts, prefabricated members, septic tanks; construction edges, building gaskets, carpet restraints, angles, louvers, etc. Use for industrial materials such as curing sheets.
Examples of agricultural / fishery / horticultural supplies include agricultural house use.
Chemical industrial products include packings, bushes, diaphragms, hydraulic hoses and the like.
Industrial and industrial materials include, for example, machine covers, machine parts, packing, gaskets, flanges, leather canvas, bolts, nuts, valves, metal protective films, and thermoplastic resin compositions such as polyethylene and polypropylene as reinforcing materials. Examples of the hose with unevenness used in combination.
Examples of the furniture include cabinets, stools, sofas, mats, curtains, table cloths, and the like.
As stationery, card cases, writing instrument cases, accessories, key cases, cash card cases, stickers, labels, book covers, notebook covers, binders, notebooks, covers, files, cards, regular items, underlays, holders, magazine trays, albums , Templates, writing instrument axes, etc.
Daily and miscellaneous goods include, for example, bath lids, slats, buckets, clothes covers, futon cases, umbrellas, umbrella covers, blinds, sewing tools, shelf boards, shelf holders, picture frames, apron, trays, tapes, strings, belts And the like.
Containers and packaging products include, for example, food containers, cap liners, cap packing, clothing packaging, packaging and packaging materials, cosmetic bottles, cosmetic containers, chemical bottles, food bottles, physics and chemistry bottles, detergent bottles, containers, caps , Food packs, laminated films, industrial shrink films, and commercial wrap films.
Examples of toys and leisure goods include toys for infants, sunglasses frames, various rackets for ball games, fastener handles, key holders, various belts, bags and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to an Example. In the following examples, “part” means “part by mass”.

Evaluation in the following examples was performed as follows.
(Measurement of crystal melting peak / crystallization peak temperature / crystallinity)
The DSC measurement was performed using a DSC220C manufactured by Seiko Denshi Kogyo Co., Ltd. at a rate of 10 ° C./min in both the temperature rising process and the temperature falling process. The crystallinity was obtained by calculation as a ratio to the value of the theoretical crystal melting calorific value, using the heat of fusion simultaneously measured when the peak temperature was measured and the peak temperature was measured.
(Measurement method of acid value)
A solution dissolved in refluxing xylene was weighed to prepare a sample, to which phenolphthalein was added as an indicator, and the acid value was determined by titrating methanolic potassium hydroxide. The end point of the titration was when the pink indicator remained for 10 seconds.

(Liquidity)
Using a melt indexer SAS-2000 manufactured by Yasuda Seiki Seisakusho, the measurement was performed at 220 ° C. and 21.17 N in accordance with ISO 1133.

(Shore A hardness)
The thermoplastic resin composition of each example was molded at a cylinder temperature of 200 ° C. by an injection molding machine with a mold clamping pressure of 50 tons manufactured by Toshiba Corporation to obtain a molded test piece of 100 mm × 100 mm × 3 mm. The hardness (Shore A) of the obtained molded specimen was measured using a Shore A type hardness meter (A type manufactured by Shimadzu Corporation) in accordance with JIS K 6253.

(Dimensional stability)
・ Difference in molding shrinkage rate The thermoplastic resin composition of each example was molded at a cylinder temperature of 200 ° C. with an injection molding machine manufactured by Toshiba Corporation with a clamping pressure of 50 tons, and a 100 mm × 100 mm × 3 mm flat plate molding was performed. A specimen was obtained.
The horizontal dimension of this flat plate test piece was measured on the flow end side and the gate side, and the shrinkage rate on the gate side was measured with the flow end side as 100%.
-Flatness The obtained flat plate test piece was placed on a horizontal work table and evaluated according to the following criteria.
◯: There is no gap between the flat plate test piece and the work table.
X: The flat plate test specimen warps and there is a gap between the work table.

(Compression set)
Using a press mold of 150 mm × 50 mm × 12.5 mm, pressing was performed at a pressing temperature of 200 ° C. and a tree pressure of 7.5 MPa to prepare a flat plate test piece.
This flat plate test piece was punched to a diameter of 29 mm to obtain a compression set test piece. Using a compression device according to JIS K6301-75, the test piece was compressed in the thickness direction until the thickness became 12.5 mm to 9.52 mm, and the compression device was placed in a constant temperature bath at 100 ° C. for 22 hours. Heated. Thereafter, the compression device was taken out of the thermostatic bath, the compression was immediately released, and the test piece was allowed to stand at 23 ° C. for 30 minutes.
The compression set was obtained from the following equation.
Compression set (%) = (original thickness of test piece−thickness after 30 minutes of compression release) / (original thickness of test piece−9.52 (mm)) × 100

(Bleed resistance)
The thermoplastic resin composition of each example was molded at a cylinder temperature of 200 ° C. with an injection molding machine manufactured by Toshiba Corporation with a clamping pressure of 50 tons to obtain a flat plate test piece of 100 mm × 100 mm × 3 mm. This test piece was heat-treated at 60 ° C. for 24 hours, and the presence or absence of oily liquid floating on the heat-treated sheet was evaluated as follows.
○: No oily liquid ×: Oily liquid present

(Stickiness)
The thermoplastic resin composition of each example was molded at a cylinder temperature of 200 ° C. with an injection molding machine manufactured by Toshiba Corporation with a clamping pressure of 50 tons to obtain a flat plate test piece of 100 mm × 100 mm × 3 mm. Ten molded specimens immediately after molding were directly stacked and allowed to stand for 30 minutes, and the peelability of each molded specimen was evaluated.
A: The molded specimens are not attached to each other at all, and the surface remains clean.
A: Molded specimens stick to each other to some extent, but peel off cleanly without scratching the surface.
○: Molded specimens stick to each other but peel off easily, and the surface is slightly scratched.
X: Molding test pieces stick to each other and do not peel off.

(Bleach treatment test)
The thermoplastic resin composition of each example was molded at a cylinder temperature of 200 ° C. by an injection molding machine manufactured by Toshiba Corporation with a clamping pressure of 50 tons to obtain a molded test piece of 20 mm × 20 mm × 3 mm. The test piece was allowed to stand at room temperature for 1 week in a mildew removing detergent containing hypochlorous acid as a main component, and then the surface appearance of the test piece was visually evaluated.
○: No change is seen at all.
X: The surface of the molded specimen deteriorates and is rough.

[Production Example 1] Production of propylene-1-butene copolymer (A-1):
Propylene-1-butene copolymer (A-1) was obtained by continuously copolymerizing propylene and 1-butene using hydrogen as a molecular weight control in a 100-liter SUS polymerizer equipped with a stirrer. Got. During polymerization, hexane as a polymerization solvent is supplied from the lower part of the polymerization vessel at a supply rate of 100 parts / hour, propylene is supplied at a supply rate of 24.04 parts / hour, and 1-butene is supplied at 1.52 parts / hour. Each was continuously fed at a speed. Further, from the lower part of the polymerization vessel, 0.005 × 10 ⁻³ parts of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride as a component of the polymerization catalyst. / time of the feed rate, triphenylmethyl tetrakis (pentafluorophenyl) borate at a feed rate of 0.298 × ^{10 -3} parts / hour, triisobutylaluminum at 2.315 × ^{10 -3} parts / feed rate Each was continuously fed.
At the same time, the reaction mixture was continuously withdrawn from the top of the polymerization vessel so that the reaction mixture in the polymerization vessel maintained an amount of 100 parts.
The polymerization temperature was 45 ° C. by circulating cooling water through a jacket attached to the outside of the polymerization vessel.
A small amount of ethanol was added to the reaction mixture continuously extracted from the upper part of the polymerization vessel to stop the polymerization reaction, followed by demonomerization and water washing, and then added to a large amount of water by steam distillation. The solvent was removed. Subsequently, the obtained undried product was dried under reduced pressure for 1 day at 80 ° C. to obtain a propylene-1-butene copolymer (A-1).
The production rate of the propylene-1-butene copolymer (A-1) was 7.10 kg / hour. The propylene monomer unit content in the propylene-1-butene copolymer (A-1) was 95.0% by mass, and the 1-butene monomer unit content was 5.0% by mass.

[Production Example 2] Production of propylene-1-butene copolymer (A-2):
A propylene-1-butene copolymer was prepared in the same manner as in Production Example 1 except that the propylene supply rate was changed to 23.52 parts / hour and the 1-butene supply rate was changed to 2.45 parts / hour. A-2) was obtained.
The propylene monomer unit content in the propylene-1-butene copolymer (A-2) was 92.0% by mass, and the 1-butene monomer unit content was 8.0% by mass.

[Production Examples 3 to 5] Production of propylene-1-butene copolymers (A-3) to (A-5):
Except having changed the quantity of propylene and 1-butene as shown in Table 1, it carried out similarly to manufacture example-1 and 2, and made propylene-1-butene copolymer (A-3)-(A-5). Obtained. These evaluation results are shown in Table 1.

[Production Example 6] Production of polypropylene resin (B-1):
Pre-contact with 0.13 part of a toluene solution having a triisobutylaluminum concentration of 1 mmol / ml and 0.065 part of a toluene solution having a concentration of dimethylsilylbis (2-methyl-1-indenyl) zirconium dichloride of 2 μmol / ml Then, it was put into an autoclave having a capacity of 100 liters.
Next, a solution prepared by dissolving 0.12 part of triphenylmethyltetrakis (pentafluorophenyl) borate in 0.058 part of toluene was charged into the autoclave and polymerized at 40 ° C. During the polymerization, propylene was continuously fed to maintain the total pressure at 0.6 MPa.
After 60 minutes, 2 parts of isobutanol was added to terminate the polymerization, and then the unreacted monomer was removed. The obtained powder was dried under reduced pressure at 60 ° C. for 5 hours to obtain 14 kg of polypropylene resin (B-1). The resulting polypropylene resin (B-1) had a melting point of 163 ° C. and a crystallinity of 70% by mass.

In addition, the following were used as the crystalline polypropylene resin (B).
(B-2): Block PPJ707G (Prime Polymer Co., Ltd.) Melting point 160 ° C., crystallinity 41 mass%
(B-3): Random PPJ227T (Prime Polymer Co., Ltd.) Melting point 149 ° C., crystallinity 33% by mass

The following were used as the acid-modified polyolefin wax (C).
(C-1): Propylene wax, PP MA1332 (Clariant Japan KK)
(C-2): Ethylene wax 2203A (Mitsui Chemicals)
(C-3): ethylene wax, A-C575A (Honeywell Corporation)
(C-4): Propylene wax, PP MA6252 (Clariant Japan KK)
(C-5): Propylene wax, A-C596A (Honeywell Corporation)
(C-6): Propylene wax, A-C1221 (Honeywell Corporation (C-7): Propylene wax, PP MA1462 (Clariant Japan Co., Ltd.)
(C-8): Ethylene wax, 1105A (Mitsui Chemicals, Inc.)
(C-9): Propylene wax, A-C597A (Honeywell Co., Ltd.) The acid value and melt viscosity of these acid-modified polyolefin waxes (C) are shown in Table 2.

The following were used as waxes (L) used as optional components.
(L-1): Unmodified ethylene wax High wax 320P (Mitsui Chemicals)
(L-2): Acid amide wax Kao wax EB-G (Kao Corporation)
(L-3): Unmodified rubber process oil Diana process oil PW380 (Idemitsu Kosan Co., Ltd.)

The following were used as another thermoplastic resin (D) used as an optional component.
TPO: Miralastomer 7030N (Mitsui Chemicals, Inc.)
TPEE-1: Hytrel # 5557M (Toray DuPont Co., Ltd.)
TPEE-2: Primalloy B1600NS (Mitsubishi Chemical Corporation)
SEBS: Tuftec 1221 (Asahi Kasei Chemicals Corporation)

Examples 1-18, Comparative Examples 1-16
Tables 3 to 6 show the propylene-1-butene copolymer (A), the crystalline polypropylene resin (B), the acid-modified polyolefin wax (C), other thermoplastic resins (D), and waxes (L). The composition was blended and melt-kneaded with a vacuum vent extruder with a screw outer diameter of 30 mm (220 ° C., 700 mmHg vacuum) to form a pellet.
The results evaluated as described above are shown in Tables 3-6.

In the thermoplastic resin compositions of Examples 1 to 18 that satisfy claim 1 of the present application, in addition to excellent fluidity, they have excellent flexibility, dimensional stability, compression set properties, low stickiness, and hypochlorous acid. A molded product capable of treating the bleaching agent as the main component was obtained.
On the other hand, in the thermoplastic resin composition of Comparative Example 1 in which the component (A) exceeded 95 parts by mass, the fluidity was low, and the compression set of the obtained molded product was low.
In the thermoplastic resin composition of Comparative Example 2 in which the component (A) was less than 30 parts by mass, the flexibility of the obtained molded product was low, and the compression set of the obtained molded product was low.
In the thermoplastic resin composition of Comparative Example 3 in which the component (C) was less than 0.3 part by mass, the obtained molded product was easily sticky.
In the thermoplastic resin composition of Comparative Example 4 in which the component (C) exceeded 10 parts by mass, the obtained molded product was easily sticky.
In the thermoplastic resin compositions of Comparative Examples 5 and 6 in which the propylene unit of the component (A) exceeded 97% by mass, the compression set characteristics of the obtained molded product were low.
In the thermoplastic resin composition of Comparative Example 7 in which the propylene unit of the component (A) was less than 90% by mass, the molded article obtained had low compression set characteristics.
In the thermoplastic resin composition of Comparative Example 8 in which the acid value of component (C) was less than 20 mg / g, the resulting molded product was easy to stick.
In the thermoplastic resin composition of Comparative Example 9 in which the acid value of the component (C) exceeded 70 mg / g, the obtained molded product was easy to stick.
In the thermoplastic resin compositions of Comparative Examples 10 to 12 in which a wax other than the acid-modified polyolefin wax was used instead of the acid-modified polyolefin wax, the obtained molded product was easy to stick.
In Comparative Example 13, which was TPO, the fluidity was low, the bleed resistance was low, and the molded product was easy to stick.
In Comparative Examples 14 and 15 which were TPEE, the obtained molded product could not be treated with a bleaching agent. Moreover, the flexibility was low.
In Comparative Example 16 in which SEBS was used in place of the component (A), the resulting molded product had low dimensional stability and compression set characteristics, and the molded product was easily sticky.

Claims (4)

30 to 95 parts by mass of an amorphous propylene-1-butene copolymer (A) composed of 90 to 97% by mass of propylene monomer units and 3 to 10% by mass of 1-butene monomer units, and crystals 5 to 70 parts by mass of the conductive polypropylene resin (B) (however, the total of the component (A) and the component (B) is 100 parts by mass), and an acid-modified polyolefin wax having an acid value of 20 to 70 mg / g ( C) and
The content of the acid-modified polyolefin wax (C) is 0.3 to 10 parts by mass with respect to 100 parts by mass in total of the propylene-1-butene copolymer (A) and the polypropylene resin. A thermoplastic resin composition.   The thermoplastic resin composition according to claim 1, wherein the polypropylene resin (B) is a propylene homopolymer.   The thermoplastic resin composition according to claim 1 or 2, wherein the acid-modified polyolefin wax (C) is an acid-modified polypropylene wax.   The molded article obtained by shape | molding the thermoplastic resin composition in any one of Claims 1-3.