JPS63251449A - Heat-resistant thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To make it possible to form a thermoplastic resin composition having excellent resistances to heat, chemicals, weather and burning, and good impact resistance and processability, by mixing a post-chlorinated vinyl chloride resin of a chlorine content in a specified range with an impact resistance improver. CONSTITUTION:This heat-resistant thermoplastic resin composition is formed by mixing 100pts.wt. post-chlorinated vinyl resin of an average chlorine content in the range of 60-64wt.% with 2-10pts.wt. impact resistance improver. As said post-chlorinated vinyl chloride resin, one having an intrinsic viscosity of 0.27-0.44 as measured by the nitrobenzene method according to JIS K-6721 is desirable. Examples of said impact resistance improver include multicomponent acrylic rubber resins, post-chlorinated polyethylenes, methyl methacrylate/butadiene/styrene resins and ethylene/vinyl acetate resins.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an easily processable heat-resistant thermoplastic resin composition. More specifically, the present invention has excellent processing suitability and is particularly suitable for containers, tanks, and piping for high-temperature chemical solutions, sewage piping for hot waste water, power cable protection pipes, etc., and has shock resistance and heat resistance. The present invention relates to a thermoplastic resin composition that provides molded products with well-balanced physical properties such as hardness and chemical resistance.

Background of the Invention Chlorinated vinyl chloride resins are known to have excellent chemical resistance, weather resistance, and flame resistance, and to have much better heat resistance than ordinary vinyl chloride resins.

However, like vinyl chloride resins, chlorinated vinyl chloride resins have the disadvantages of low impact resistance, high melt viscosity, and difficulty in processing.

Therefore, when using post-chlorinated vinyl chloride resin as a material for containers, tanks, piping for high-temperature chemical solutions, sewage piping for hot waste water, electrical cable protection pipes, etc., it cannot be used as is, so the resin There is a need to improve the above drawbacks by incorporating various modifiers.

So far, there have been products containing such modifiers, such as those in which a specific amount of chlorinated polyolefin is blended with post-chlorinated vinyl chloride resin (Japanese Patent Publication No. 38-12175), and those containing acrylic acid alkyl esters. Compounds of multi-component resins obtained by copolymerizing styrene and methyl methacrylate have been proposed (Japanese Patent Publication No. 18230/1983), but improvements in processability and impact resistance have not yet been achieved. The current situation is that this has not been achieved.

Problems to be Solved by the Invention Under these circumstances, the present invention provides a material that has excellent heat resistance, chemical resistance, weather resistance, and flame resistance, as well as good impact resistance and processability. The purpose of this invention is to provide a thermoplastic resin composition mainly composed of chlorinated vinyl resin.

Means for Solving the Problems The present inventors have conducted intensive research on post-chlorinated vinyl chloride resins in order to improve their impact resistance and processability. We have discovered that the above object can be achieved by blending an impact modifier in a predetermined ratio with a chlorinated vinyl chloride resin, and based on this knowledge, we have completed the present invention. Ta.

That is, the present invention provides (A) a post-chlorinated vinyl chloride resin with an average chlorine content of 60 parts by weight or more and less than 64 parts by weight.
The object of the present invention is to provide a heat-resistant thermoplastic resin composition having good processability, which contains 2 to 10 parts by weight of the impact modifier (B) per 0 parts by weight.

The present invention will be explained in detail below.

In the composition of the present invention, a post-chlorinated vinyl chloride resin is used as the component (A), and the post-chlorinated vinyl chloride resin has an average chlorine content of 60% by weight and 64% by weight.
It must be less than Such a product can be produced by appropriately adjusting the chlorination conditions in a known method, for example, a method in which vinyl chloride resin powder is chlorinated in a gas phase or suspended in water.

If the average chlorine content is less than 60% by weight, it will not be possible to obtain a product with sufficient heat resistance, and if it is more than 64% by weight, the melt viscosity will be high and the processability will be poor. impact resistance tends to decrease. In addition, the intrinsic viscosity of the post-chlorinated vinyl chloride resin measured by the nitrobenzene method according to JISK-6721 is 0°27 to 0.44 in order to improve the processability of the composition and the impact resistance of the molded product. Preferably within this range.

The vinyl chloride resin used in the subsequent production of the chlorinated vinyl chloride resin may be a vinyl chloride homopolymer or a vinyl chloride copolymer with other monomers that can be copolymerized with vinyl chloride. However, when using a copolymer, the content of other copolymerizable monomers is 15 parts by weight or less, preferably 6 parts by weight or less, based on 100 parts by weight of vinyl chloride units. Good. Examples of other copolymerizable monomers include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl laurate; acrylic esters such as methyl acrylate, ethyl acrylate, and butyl acrylate; and methyl methacrylate and ethyl methacrylate. Methacrylic acid esters, maleic esters such as diptyl maleate and diethyl maledna, fullal acid esters such as dibutyl fumarate and diethyl fumarate, vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether, acrylonitrile, methacrylate trile, etc. Examples include vinyl cyanides, olefins such as ethylene, propylene, and n-butene, vinylidene halides other than vinyl chloride, such as vinylidene chloride, and vinyl bromide, and vinyl halides.

Impact modifiers used as component (B) in the composition of the present invention include multi-component acrylic rubber resins, post-chlorinated polyethylene, methyl methacrylate/phtadiene/styrene resins, and ethylene/vinyl acetate resins. be. Among these, the multicomponent acrylic rubber resin includes, for example, a multicomponent resin obtained by graft-polymerizing monomers such as methyl methacrylate, styrene, and acrylonitrile to a copolymer rubber mainly composed of acrylic acid ester. This multi-component resin is produced by a known method, for example, by reacting an acrylic acid argyl ester having an alkyl group with 2 to 8 carbon atoms with a copolymerizable monovinyritine compound and a polyfunctional crosslinking agent, and first producing a rubber-like resin. An aqueous dispersion of the polymer is prepared, and then, to 20 to 80 parts by weight of this rubbery copolymer, a methacrylic acid alkyl ester whose alkyl group has 1 to 4 carbon atoms, a vinyl aromatic compound, an unsaturated nitrile, and these are added. Produced by a method such as graft polymerization of 80 to 20 parts by weight of a monomer mixture for granod consisting of all or 2 to 6 monomers containing a monovinylidene group copolymerizable with the monomer of Can be done.

Commercial products of such multi-component acrylic rubber resins include, for example, Kureha HIA-15, HIA-28 (manufactured by Gugen Kagaku Co., Ltd., trade name), Kane Ace FM (manufactured by Kanebuchi Chemical Co., Ltd., trade name). ], Metaprene W-300, W-529
[Mitsubishi Rayon (made by scooping, product name]) etc.

In addition, as the post-chlorinated polyethylene, it is possible to appropriately select and use from known ones, but in particular, the chlorine content is 2.
Suitable materials include 0 to 450 to 45 parts by weight or 60 to 400 to 40 parts by weight and are amorphous. A commercially available product of such post-chlorinated polyethylene is, for example, Elasrene 301A.

351A, 401A (manufactured by Showa Denko K.K., product name)
, Guisolac H-j35 (manufactured by Osaka Soda, trade name), CPE-3614, 3615 (manufactured by Dow Chemical Company,
product name) etc.

In addition, the methyl methacrylate/butadiene/styrene resin is a multicomponent resin obtained by a known method, such as a method in which methyl methacrylate, styrene, etc. are graft-polymerized onto a rubber whose main component is butadiene.
MBS resin) or the like can be used. Commercially available MBS resins include, for example, Metaprene C-
223 (manufactured by Mitsubishi Rayon Co., Ltd., product name), Suren B
Examples include TA-111Nx C (manufactured by Gugen Kagaku Co., Ltd., trade name) and Kanerikyo Ace B-56 (manufactured by Kanefuchi Kagaku Co., Ltd., trade name).

Furthermore, ethylene/vinyl acetate resin (EVA resin)
As such, those containing 18 to 40 moles of vinyl acetate units are suitable. Commercially available products such as these include:
For example, Evaflex 250, Evaflex IM12
, Elvaloy 867, 868 [Mitsui Polychemical (manufactured by Kiki, trade name)], etc.

These impact resistance modifiers may be used alone or in combination of two or more, and the blending amount is as follows:
The amount is selected in the range of 2 to 10 parts by weight based on 100 parts by weight of the post-chlorinated vinyl chloride resin of component (A). If this amount is less than 2 parts by weight, the effect of improving impact resistance and processability will not be sufficiently exhibited, while if it exceeds 10 parts by weight, heat resistance and mechanical strength will decrease. When a multi-component acrylic rubber resin or post-chlorinated polyethylene is used as the impact modifier, the amount thereof is preferably in the range of 6 to 10 parts by weight.

Various additives such as stabilizers, lubricants, antioxidants, fillers, ultraviolet absorbers, colorants, etc. can be added to the composition of the present invention, if necessary.

Examples of the stabilizer include lead-based stabilizers such as tribasic lead sulfate and dibasic lead phosphite, butyl tin malate, butyl tin laurate, butyl tin mercaptide, octyl tin maleate, octyl tin mercaptide, and methyl. Examples include tin-based stabilizers such as tin mercaptide, and examples of lubricants include metal soaps such as lead stearate, cadmium stearate, zinc stearate, and calcium stearate, paraffin wax, microcrystal waracas, polyethylene waracas, fatty acid,
Fatty acid amides, fatty acid esters, aliphatic ketones, fatty alcohols, fatty acid partial ester waxes, etc. are used as antioxidants, such as phenyl-α-naphthylamine, phenyl-β-naphthylamine, aldol-α-
Naphthylamine type such as nanothylamine, diphenylamine L2,2 such as p-impropoxy-diphenylamine, NIN'-diphenyl-propylene diamine, etc.
．． 4-trimethyl-1,2-dihydroquinone polymer,
Quinolines such as 6-nitoxy2.2.4-trimethyl-1,2-dihydroquinoline, 1-oxy-6-methyl-4-isopropylbenzene, 2,6-di-tert-butyl-4-methylphenol, etc. monophenolics,
4.4'-dihydroxydiphenyl, hindered bisphenol, tris-(2-methyl-4-hydroxy-5
-Polyphenols such as -tert-butylphenyl)butane, thiobisphenols such as 4-4'-thiobis-(6-tert-butyl-6-methylphenol), etc.
Examples of fillers include calcium carbonate, aluminum silicate, aluminum hydroxide, magnesium carbonate, magnesium hydroxide, diatomaceous earth, wood flour, talc, silica, mica, etc.; examples of ultraviolet absorbers include phenyl salicylate, p- Salicylic acid derivatives such as octerphenyl salicylate, benzophenones such as 2,4-dihydroxybenzophenone, 2-hydro+1y-4-methoxybenzophenone, 2-(2'-hydroxy-
5'-Methyl-phenyl)penztriazole, 2-(
Triazoles such as 2'-hydroxy-31,51-di-tertiary-butyl-phenyl)benzotriazole, resorcinol monobenzony), 2,4-di-tertiary-
Butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, methyl o-benzoylbenzoate, etc., and examples of coloring agents include titanium oxide, lead white, lithopone, pallite, carbon black, cadmium red, red iron. Examples include inorganic pigments such as , silver vermillion, and cadmium yellow, azo pigments, nitroso pigments, nitro pigments, basic dye lakes, and phthalocyanine pigments.

The amount of these additives can be arbitrarily selected within a range that does not impair the purpose of the present invention, but usually based on the total weight of components (A) and (B),
Stabilizer: 5% by weight or less, lubricant: 0.5 to 5% by weight, antioxidant: 2% by weight or less, filler: 100% by weight or less, ultraviolet absorber: 2% by weight or less, colorant: 6% by weight or less selected within the range.

The composition of the present invention can be prepared by mixing the above-mentioned (A) component, (B) component, and various additives used as necessary with a high-speed mixer such as a Henschel mixer or a super mixer, a ribbon blender, a Banbury mixer-1 continuous mixer, etc. It can be prepared by putting it into a mixer such as a mixing roll or a laikaiki and mixing it uniformly at an appropriate temperature.

The thermoplastic resin composition of the present invention prepared in this manner preferably has a hot melt viscosity of 319 m or less from the viewpoint of processability.

Effects of the Invention The thermoplastic resin composition of the present invention has excellent heat resistance, chemical resistance, weather resistance, flame resistance, as well as impact resistance and processability, which are inherent to post-chlorinated vinyl chloride resins. For example, it is particularly suitable as a material for containers, tanks, piping for high-temperature chemical solutions, sewage piping for heated waste water, electrical cable protection pipes, etc. Furthermore, it is also suitable for use as window plates for plating tanks, chlorine gas piping, reaction tanks, etc. It is also useful for applications such as window frames, wall boards, pipes, and other building and construction components.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited in any way by these examples.

In addition, each physical property of the composition was evaluated according to the following method.

Preparation of test pieces The powdered compound was kneaded for 7 minutes at 180 tons using an 8-inch roll mixer to obtain a sheet of approximately 0.55 mm. Next, 2 or 6 of these sheets were mixed in alternating vertical and horizontal directions. They were stacked so as to have the following shapes and press-molded at 190°C to obtain plate-shaped bodies each having a thickness of j txw or 3sty, and then test pieces were cut from each of the plate-shaped bodies.

(1) Impact resistance A Charpy impact test was conducted in accordance with JIS K-7111 to determine impact resistance. Note that the test piece was cut out from a plate with a thickness of 1 mm.

(2) Heat resistance A flexibility temperature test was conducted in accordance with JIS K-6745 to determine heat resistance. Note that the test piece was cut out from a plate-shaped body with one spacer.

(6) Fill 57 g of the powdered compound with melt viscosity and sustained heat stability into a rotor tank of a Brabender Plastograph machine whose temperature was pre-controlled at 200°C, and rotate the kneader at 5 Q rpm. The compound is melt-kneaded, the melt resistance value (torque, kg-77+) in the stable state is taken as the melt viscosity value, and the time (6) from the start of gelation of the compound to the start of thermal decomposition is the sustained thermal stability. The value was taken as the gender value.

(4) Roll sheet gelation properties Mixing rolls (2 rolls) with an 8-inch diameter and 20-inch length preset at 180°C at 15 rpm and IB
Rotate at rpm and add 150 powder powder to this
! 7 was filled and kneaded to form a sheet, the roll processability at that time was observed, and the roll sheet gelability was evaluated according to the following criteria.

(a) Time from powder to rolled into sheet.

Within 1 minute 201 to less than 2 minutes: ■ 2 to less than 6 minutes: △ 6 minutes or more: × (B) After being wrapped in a sheet, after 60 minutes of crosstalk,
Observe the peeling state of the sheet.

Good peelability 20" Slightly poor: ■ " Bad: △ Adhesive to roll: × (5) Chemical resistance A 60 weight percent chromic acid aqueous solution, an 80 weight percent sulfuric acid aqueous solution, and a 20 weight percent nitric acid aqueous solution were prepared. , set the liquid temperature to 60
℃, test pieces (25X80X3
Question) was soaked for 2 weeks, washed with running water for 2 hours, kept in a desiccator for 48 hours, and its flexural modulus was determined.
Measurement was conducted in accordance with K-7203, and chemical resistance was evaluated in accordance with the following criteria.

Change in elastic modulus is less than 5q6 205 to less than 10%: △ 10% or more: × Examples 1, 2, Comparative Examples 1, 2 Average chlorine content 61o8 weight ratio chlorinated vinyl chloride resin (CPVC) 100 parts by weight, MBS resin as impact modifier [Fure...BTA lTlNx %
Manufactured by Gugen Kagaku Co., Ltd.) 0, 4, 8.12 parts by weight, stabilizer (
Tribasic lead sulfate] 6 parts by weight and lubricant (lead stearate)
1 part by weight was mixed for 15 minutes at 120° C. using a sieve machine, taken out and cooled to prepare a powdery compound, and the lactic properties of this compound were determined. The result is the first
Shown in the table.

In addition, Comparative Example 1 is when the MBS resin content is 0, Examples 1 and 2 are 4 and 8 parts by weight, respectively, Comparative Example 2 is
is the case of 12 parts by weight.

Comparative Example 6 In Example 2, instead of CPVC with an average chlorine content of 61°8 weight ratio, CPVC with an average chlorine content of 66.6% by weight and PVC (chlorine content 56°8% by weight) were used in the weight ratio. A powdered compound was prepared in the same manner as in Example 2, except that a blend of 50,150% (average chlorine content: 61.6% by weight) was used, and its characteristics were determined. The results are shown in Table 1.

Examples 6 and 4, Comparative Examples 4 and 5 Examples 1 and 2, respectively, except that CPVC with an average chlorine content of 66.6% by weight was used instead of CPVC with an average chlorine content of 61.8% by weight. Powdered compounds were prepared in the same manner as in Comparative Examples 1 and 2, and their physical properties were determined. The results are shown in Table 1.

Comparative Example 6 In Comparative Example B, the average chlorine content is 6°3 weight ratio C
The blend ratio of PVC and PvC is 70/6 on a weight basis.
A powdery compound was prepared in the same manner as in Comparative Example 6, except that the average chlorine content of the blend was changed to 0 (average chlorine content of the blend: 63.5% by weight), and its physical properties were determined. The results are shown in Table 1.

Examples 5 to 8, Comparative Examples 7 to 10 Instead of using MBS resin as an impact modifier, multi-component acrylic rubber resin [Fure...formerly A-28, Guji Kagaku (made from silk)] was used. Powdered compounds were prepared in the same manner as in Examples 1 to 4 and Comparative Examples 2, 3, 5, and 6, respectively, and their physical properties were determined.The results are shown in Table 2.

Examples 9 to 12, Comparative Examples 11 to 14 Instead of using MBS resin as an impact modifier,
Post-chlorinated polyethylene [Showa Denko to Elaslene 651 (
Powdered compounds were prepared in the same manner as in Examples 1 to 4 and Comparative Example 2.3.5.6, respectively, except that the compound manufactured by Co., Ltd. was used, and their physical properties were determined. The results are shown in Table 3.

Examples 16-16, Comparative Examples 15-18 Instead of using MBS resin as an impact modifier, E
Examples 1 to 4, respectively, except that VA-based resin [Evaflex 11250, manufactured by Mitsui Polychemical Co., Ltd.] was used.
．． Powdered compounds were prepared in the same manner as in Comparative Examples 2, 3, and 5.6, and their physical properties were determined. The results are shown in Table 4.

Procedural amendment band May 7, 1988 Commissioner of the Patent Office Black 1) Akio Yu 1, Indication of the case Patent Application No. 83003 of 1983 2, Name of the invention Heat-resistant thermoplastic resin composition 3, Person making the amendment Relationship to the incident Patent applicant: 3-3-1 Marunouchi, Chiyoda-ku, Tokyo Representative: Tadashi Kamiya - 4, agent telephone: (591) 991.0-1;', V1 Yumi' - To 5,
Date of amendment order: 6, Number of inventions increased by amendment: 0 8, Contents of amendment (1) Specification, page 8, line 5, and page 9, lines 2 to 3
Correct line 1 "Mitsubishi Rayon" to "Mitsubishi Rayon."

(2) 1 money power ace B-56 in the 4th row of the 9th peno
Correct it to 1 Money Ace B-564.

(3) 1 crystal wax of "crystal wax, polyethylene wax" in line 15 of the 10th peno.
Corrected to "Polyethylene wax."

(4) In the 7th line of page 13, 1 Laikaiki” is corrected to 1.

(5) 1 test piece on the second line from the bottom of page 14 is 1yu
Correct J to 1 test piece is 3 m.

(6) In the Comparative Example 10 column of Table 2 on page 21, the sustained thermal stability term (,oi,,)r△” in the physical property evaluation is set to “10”.
We will correct the rating from ``10'' to ``△''.

Claims (1)

[Scope of Claims] 1(A) Based on 100 parts by weight of post-chlorinated vinyl chloride resin having an average chlorine content of 60% by weight or more and less than 64% by weight,
(B) containing 2 to 10 parts by weight of an impact modifier;
A heat-resistant thermoplastic resin composition with good processability. 2 The post-chlorinated vinyl chloride resin conforms to JISK-6721
Intrinsic viscosity 0 according to the nitrobenzene method measured according to the method. 27-0. 44. The composition according to claim 1, which has a molecular weight of 44. 6. Claim No. 6, wherein the impact modifier is at least one selected from a multicomponent acrylic rubber resin, a post-chlorinated polyethylene, a methyl methacrylate-butadiene-styrene resin, and an ethylene-vinyl acetate resin. 1
The composition according to item 1 or 2. 4. The composition according to claim 1, 2 or 3, which has a hot melt viscosity of 3 kg·m or less.