JPH05186650A - Vinyl chloride-based resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, composed of a vinyl chloride-based polymer, acrylonitrile-butadiene-styrene resin, etc., in a specified proportion, excellent in impact resistance, tensile strength, moldability and glossiness, having low toxicity and useful as moldings, etc. CONSTITUTION:The objective composition is composed of (A) 100 pts.wt. vinyl chloride-based polymer having 500-2500 average degree of polymerization (B) 4-15 pts.wt. acrylonitrile-butadiene-styrene resin or methyl methacrylate- butadiene-styrene resin, (C) 1-7 pts.wt. styrene-butadiene rubber, (D) 1-10 pts.wt. acrylonitrile-styrene copolymer and (E) 0.1-10 pts.wt. polyorganosiloxane.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition which gives a molded article having good processability and excellent impact resistance.

[0002]

2. Description of the Related Art Conventionally, for the purpose of improving the impact strength of a molded product obtained from a vinyl chloride resin, a vinyl chloride resin is acrylonitrile / butadiene / styrene resin (hereinafter referred to as ABS resin, hereinafter the same), methylmethacryl acid·
Butadiene / styrene resin (MBS resin), ethylene-
Attempts have been made to add and blend impact strength improvers such as vinyl acetate copolymer (EVA resin) and styrene-butadiene rubber (SBR).

When ABS resin, MBS resin or SBR is used as the impact strength improver, it is obtained because the double bond contained in the molecule is active against light, ultraviolet ray or heat. The molded product has poor weather resistance. As measures against this, it has been proposed to add an antioxidant, an ultraviolet absorber or the like, but even with this addition, it is not possible to obtain various physical properties. Also,
When EVA resin is used and the molding temperature is raised or the residence time is lengthened, the vinyl chloride resin and EVA resin are melted uniformly and the impact strength is lowered, so that it is complicated to adjust molding conditions such as temperature control. There was a drawback that

On the other hand, in a vinyl chloride resin composition, a large amount of an inorganic filler is blended with a vinyl chloride resin for the purpose of imparting flame retardancy to a molded product obtained from the resin. However, as the amount of addition increases, various physical properties such as impact strength and tensile strength of the molded product obtained from this gradually decrease.Most of the fillers are fine particle powders. Since the friction coefficient between the two is small, when a vinyl chloride resin composition containing these is extruded using an extruder, the amount of extrusion at a constant temperature and pressure decreases, and the residence time in the extruder becomes longer. There is a disadvantage that the quality of the obtained molded product is adversely affected and unfavorable results such as burns and plate-out are brought about.

[0005]

As described above, a vinyl chloride resin which is excellent in molding workability, has good physical properties such as impact resistance and tensile strength, and gives a molded product having a well-balanced and satisfactory appearance. The composition has not yet been found. Therefore, an object of the present invention is to provide a vinyl chloride resin composition which solves the above-mentioned conventional drawbacks and provides a molded article having excellent physical properties such as impact resistance and tensile strength. ..

[0006]

The vinyl chloride resin composition according to the present invention comprises: A) 100 parts by weight of a vinyl chloride polymer having an average degree of polymerization of 500 to 2500; and B) 4 to 15 parts by weight of ABS resin or MBS resin. , C) 1 to 7 parts by weight of SBR, D) acrylonitrile-styrene copolymer (AS copolymer) 1 to 10
Parts by weight and E) 0.1 to 10 parts by weight of polyorganosiloxane, more preferably AB as component B
Graft-polymerization type S- or MBS resin containing 40 to 80% by weight of butadiene, SBR as C component, styrene-butadiene-styrene block copolymer of styrene and butadiene ratio
What is contained in the ratio of 30:70 to 50:50 in the AS copolymer as the D component, those containing 10 to 30% by weight of acrylonitrile, in addition to the polyorganosiloxane as the E component, polydimethyl A siloxane or polydimethylsiloxane in which a part of the methyl groups bonded to silicon is substituted with an olefin having 2 to 16 carbon atoms or α-methylstyrene is used, respectively.

The present invention will be described in detail below. The vinyl chloride polymer used as the component A in the vinyl chloride resin composition of the present invention has an average degree of polymerization of 500 to 2500,
Preferably 800 to 1700 vinyl chloride homopolymer, copolymer containing vinyl chloride in an amount of 50% by weight or more and a vinyl monomer copolymerizable therewith, and vinyl chloride and various polymers or polyvinyl chloride. A graft polymer of (PVC) and a vinyl monomer is included.

As the copolymerizable vinyl monomer, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-
Nonene, 1-decene, 1-undecene, 1-dodecene,
Α-Olefin such as 1-tridecene and 1-tetradecene; acrylic acid such as acrylic acid, methyl acrylate and ethyl acrylate, or an ester thereof; methacrylic acid,
Methacrylic acid or its esters such as methyl methacrylate; maleic acid or its esters; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as lauryl vinyl ether and isobutyl vinyl ether; maleic anhydride; acrylonitrile; styrene; vinylidene chloride and the like. These are used alone or in combination of two or more. Further, as the graft polymer, ethylene / vinyl acetate copolymer-vinyl chloride graft polymer, ethylene / propylene rubber-vinyl chloride graft polymer, PVC-styrene graft polymer, PVC-butadiene graft polymer, PV
A C-methyl methacrylate graft polymer etc. are illustrated.

Among these vinyl chloride polymers, those having an average degree of polymerization of less than 500 are inferior in impact strength and tensile strength,
Exceeding 2500 results in high extrusion torque during molding and high viscosity of the molten polymer, resulting in poor processability, resulting in significant heat deterioration due to high temperature, and It is not preferable because the physical properties are deteriorated.

The ABS resin and MBS resin as the component B are used in an amount of 4 to 15 parts by weight, preferably 7 to 12 parts by weight, based on 100 parts by weight of the vinyl chloride polymer. If this content is less than 4 parts by weight, the effect of improving impact resistance cannot be obtained.
When it exceeds the weight part, various properties such as heat resistance, tensile strength and fluidity are deteriorated, and the appearance of the molded product during extrusion is deteriorated, which is not preferable. Further, it is preferable that both the ABS resin and the MBS resin are graft type and the butadiene content is 40 to 80%. This is 80
When the content exceeds 40% by weight, the impact resistance is good, but it causes deterioration of fluidity and tensile strength. When the content is less than 40% by weight, the impact resistance cannot be improved.

The SBR used as the component C is used in an amount of 1 to 7 parts by weight, preferably 2 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride polymer. If it is less than 1 part by weight, the fluidity-improving effect cannot be obtained and the workability is deteriorated, and the appearance of the obtained molded product is frayed, and if it exceeds 7 parts by weight, the impact resistance is decreased and VICAT softening is caused. Physical properties such as dots are also reduced. The SBR is a block copolymer of styrene-butadiene-styrene, in which the weight ratio of styrene to butadiene is 30:70 to 60:40, especially 35:
Those contained at 65 to 60:40 are preferable.

The AS copolymer as the component D is used in an amount of 1 to 10 parts by weight, preferably 3 to 7 parts by weight, based on 100 parts by weight of the vinyl chloride polymer. If it is less than 1 part by weight, the effect of improving tensile strength cannot be obtained, and if it exceeds 10 parts by weight, impact resistance may be deteriorated. Further, this AS copolymer comprises acrylonitrile and styrene in a weight ratio of 10: 90-3.
It is preferable that the content is 0:70, particularly 20:80 to 25:75. If the amount of acrylonitrile in this copolymer is less than 10% by weight, the compatibility with the resin may decrease and separation may occur, and if it exceeds 30% by weight, the fluidity may decrease.

As described above, the polyorganosiloxane as the component E is a polydimethylsiloxane, or a part of the methyl group bonded to silicon of the polydimethylsiloxane is substituted with an olefin having 2 to 16 carbon atoms or α-methylstyrene. Further, it is an alkyl-modified polydimethylsiloxane or an α-methylstyrene-modified polydimethylsiloxane and is represented by the following general formula 1.

[Chemical 1]

The polyorganosiloxane is used in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the vinyl chloride polymer. If the amount is less than 0.1 part by weight, the effect of modifying the fluidity cannot be obtained, and the appearance of the obtained molded product will be frayed. On the other hand, if it exceeds 10 parts by weight, physical properties such as tensile strength may be deteriorated, which is not preferable. Also, this polyorganosiloxane has a viscosity at 25 ° C of 100-7000cs, especially 300-7000cs.
It is preferable to use the one of 2000cs. Among the above polyorganosiloxanes, the alkyl-modified polydimethylsiloxane and the α-methylstyrene-modified polydimethylsiloxane are effective for improving the impact resistance and tensile strength of the obtained molded product, and particularly the modification ratio [n / (n + m ) × 100 mol%] is preferably 30 to 80 mol%. Further, an alkyl-modified polydimethylsiloxane having 4 to 16 carbon atoms is particularly preferable because it has excellent extrusion characteristics.

The vinyl chloride resin composition according to the present invention is
In addition to the above A to E components, if necessary, stabilizers, stabilizing aids, lubricants, inorganic fillers, ultraviolet absorbers, antioxidants and the like can be added. The stabilizer is not particularly limited as long as it can be blended with a general vinyl chloride resin, laurate-based, malate-based, mercaptide-based organotin stabilizers, Ca, Ba, Pb and other metal soap stabilizers, etc. These are used alone or in combination of two or more. Epoxy compounds as stabilizers, pure hydrocarbons such as paraffin wax and polyethylene wax as lubricants, fatty acids such as palmitic acid and stearic acid, aliphatic alcohols such as stearyl alcohol, esters of fatty acids and alcohols. Examples of such compounds include a system and a partial ester system of a fatty acid and a polyhydric alcohol. Calcium carbonate is preferable as the inorganic filler, and both heavy calcium carbonate and light calcium carbonate can be used. When importance is attached to impact resistance, it is preferable to add a large amount of light calcium carbonate.

[0016]

EXAMPLES Hereinafter, specific embodiments of the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Examples 1 to 4 and Comparative Examples 1 to 10. The ingredients shown in Table 1 were mixed uniformly at 120 ° C using a Henschel mixer, and each mixture was 20 mmφ.
Was extruded into pellets using a single screw extruder of, and then extruded into sheets using the same single screw extruder. Table 2 shows the measurement results of the torque, pressure, and extrusion amount at that time, and the results of evaluation by the following method by observing the gloss of the surface of the sheet and the flaking state of the edge of the sheet. In addition, the resin obtained with the Henschel mixer was heated at 170 ° C for 5 hours using a 6-inch roll.
After kneading for a minute, a sheet having a thickness of 0.8 mm was prepared. Using this, an impact resistance test and a tensile strength test were conducted, and the results are shown in Table 3.

Details of each component used are as follows.・ Polyvinyl chloride resin (abbreviated as POS in the table): TK-400 (Shin-Etsu Chemical Co., Ltd., average degree of polymerization 400) TK-1000 (〃, 〃 1000) TK-2500P (〃, 〃 3000) ・ ABS resin (Abbreviated as ABS in the table): BLENDEX 467 (G
Company E, graft polymerization type, butadiene content 65% by weight) ・ MBS resin (abbreviated as MBS in the table): Metablen C-2
23 (manufactured by Mitsubishi Rayon Co., graft polymerization type, butadiene content 65 wt%) SBR resin (abbreviated as SBR in the table): TRKX-138S (Shell Chemical Co., styrene-butadiene-styrene block copolymer, Styrene: Butadiene = 40:60 [weight ratio] AS resin (abbreviated as AS in the table): FD (manufactured by Daicel Chemical Industries, acrylonitrile: styrene = 23:77 [weight ratio]) Polyorganosiloxane (table Middle, abbreviated as POS): KF
-412 (Shin-Etsu Chemical Co., Ltd., a mixture of polydimethylsiloxane modified with an alkyl group having 12 to 14 carbon atoms at a modification rate of 72 mol%, viscosity: 500cs [25 ° C]) KF-410 (same as above, α -Polydimethylsiloxane modified with methylstyrene at a modification rate of 39 mol%, viscosity: 1000cs
[25 ℃]) KF-96 (Same as above, polydimethylsiloxane, viscosity: 5000cs
[25 ℃]) Stabilizer: Stabilizer (TM-181SFJ, manufactured by Katsuta Kako Co., Ltd.,
Organic tin stabilizer) 〃 (calcium stearate) ・ Inorganic filler: Inorganic filler (Shiragika CCR, calcium carbonate from Shiraishi Calcium Co., Ltd.) 〃 (CR-60, same as before, titanium dioxide)

The details of the test method used are as follows. -Evaluation method of gloss on the surface of the sheet: The gloss state was evaluated in 6 grades, with 5 being glossy and excellent and 0 being no gloss at all. -Evaluation method of swelling state at the edge of the sheet: The case where there is no swelling was set to 5, and the case where the swelling was remarkable, was set to 0, and the swelling state was evaluated in 6 stages. -Impact resistance test: Four sheets of 0.8 mm thickness described above are stacked and pressed to form a sheet of 3 mm thickness, JIS K-71
Measured based on 10.・ Tensile strength test: 4 sheets of 0.8mm thickness mentioned above are piled up and pressed to make 3mm thickness sheet, JIS K-7206
It was measured based on.

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

[Table 3]

[0022]

INDUSTRIAL APPLICABILITY The vinyl chloride resin composition of the present invention can be easily molded by an ordinary extruder, and the molded product obtained has excellent physical properties such as impact strength and tensile strength and is nontoxic. In addition, the surface is smooth and glossy.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication C08L 55/02 LME 7142-4J (C08L 27/06 55:02 53:02 83:04 25:12 ) (C08L 27/06 25:12 83:04 55:02 51:04)

Claims (5)

[Claims] 1. A) 100 parts by weight of a vinyl chloride polymer having an average degree of polymerization of 500 to 2500, B) 4 to 15 parts by weight of acrylonitrile-butadiene-styrene resin or methylmethacrylic acid-butadiene-styrene resin, and C) styrene. A vinyl chloride resin composition comprising 1 to 7 parts by weight of butadiene rubber, 1 to 10 parts by weight of D) an acrylonitrile / styrene copolymer, and E) 0.1 to 10 parts by weight of polyorganosiloxane. 2. An acrylonitrile-butadiene-styrene resin or a methylmethacrylic acid-butadiene-styrene resin is a graft polymerization type and contains 40 to 60 parts of butadiene.
The vinyl chloride resin composition according to claim 1, which contains 80% by weight. 3. A styrene-butadiene rubber is styrene-
The vinyl chloride resin composition according to claim 1, which is a butadiene-styrene block copolymer and contains styrene and butadiene in a weight ratio of 30:70 to 60:40. 4. An acrylonitrile-styrene copolymer,
The vinyl chloride resin composition according to claim 1, which contains 10 to 30% by weight of acrylonitrile. 5. A polyorganosiloxane in which polymethylsiloxane or a part of a methyl group bonded to silicon of polydimethylsiloxane is substituted with an olefin having 2 to 16 carbon atoms or α-methylstyrene. Item 2. A vinyl chloride resin composition according to item 1.