JPS63251447A - Heat-resistant polyvinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To make it possible to form a polyvinyl chloride resin composition improved in heat resistance, especially, Vicat softening point, by mixing a vinyl chloride/o-chlorophenylmaleimide copolymer with additives containing a stabilizer. CONSTITUTION:This resin composition comprises at least 60wt.% vinyl chloride/ o-chlorophenylamaleimide copolymer (a) containing 0.2-40wt.% o- chlorophenylmaleimide monomer units and at most 40wt.% additives (b) containing at least a stabilizer, wherein additives which are liquid at normal temperature amount to at most 5wt.% of the total composition. It is desirable that the degree of polymerization of component (a) is 300-3,000.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a heat-resistant polyvinyl chloride resin composition.

[Conventional technology]

Vinyl chloride resins are widely used because hard, semi-hard, or soft products can be obtained by kneading them with stabilizers, lubricants, fillers, colorants, and the like.

In the hard field, it is used in a variety of applications such as corrugated sheets, pipes, decking materials, building materials, cable ducts, and joint plates.

In recent years, these molded products are required to have heat resistance. A blend composition of a vinyl chloride homopolymer and a heat-resistant polymer disclosed in 1996 has been highly praised.

[Problem that the invention seeks to solve]

However, since the above method is an attempt to obtain a composition by blending different types of polymers, such as a vinyl chloride homopolymer and a heat-resistant polymer, which inherently lack compatibility, there is a problem in that it is difficult to obtain a uniform molded product. Ta. When only a vinyl chloride homopolymer is used, the above-mentioned problems can be avoided because different types of polymers that inherently lack compatibility are not used, but an improvement in the Vicat softening point cannot be expected.

[Means for solving problems]

The present inventors have conducted extensive research to solve the above problems, and have completed the present invention.

That is, the heat-resistant polyvinyl chloride resin composition of the present invention contains 0.2 orthochlorophenylmaleimide monomer units.
consisting of 60% by weight or more of an orthochlorophenylmaleimide-vinyl chloride copolymer containing ~40% by weight, and (b) 40% by weight or less of an additive containing at least a stabilizer, and
It is characterized in that the additive that is liquid at room temperature accounts for 5% by weight or less of the entire composition.

The vinyl chloride copolymer used in the present invention can be obtained by copolymerizing orthochlorophenylmaleimide and vinyl chloride, but the polymerization itself may be carried out in accordance with a known vinyl chloride polymerization method, for example, 30 to 75° C suspension polymerization method, bulk polymerization method, emulsion polymerization method, solution polymerization method, and the like.

The heat-resistant polyvinyl chloride resin composition of the present invention includes:
Orthochlorophenylmaleimide' monomer unit is 0.2
~40% by weight of vinyl chloride copolymer containing 60% by weight
It must contain at least a stabilizer, and if necessary, a lubricant, filler, and other additives.
For example, colorants, plasticizers, other resins, etc. may be included in an amount not exceeding 40% by weight, but additives that are liquid at room temperature need to be 5% by weight or less of the entire composition.

In the heat-resistant polyvinyl chloride resin composition described above,
It is more preferable that the vinyl chloride copolymer accounts for 70% by weight or more and the other substances account for 30% by weight or less, and more preferably 80% by weight or more and 720% by weight or less, respectively. If the vinyl chloride copolymer content is less than 60% by weight, the Vicat softening point will not be improved sufficiently and cannot be used.

The orthochlorophenylmaleimide monopodal unit in the vinyl chloride copolymer is preferably 0.2 to 40% by weight, and 0.5% by weight.
-30% by weight is more preferred, and 1.0-30% by weight is most preferred. If it is less than 0.2% by weight, the improvement in the Vicat softening point is negligibly small, and if it is more than 40% by weight, workability deteriorates, which is not preferable.

The amount of orthochlorophenylmaleimide monomer units (y, weight %) in the copolymer was determined from the elemental analysis value of chlorine (X, weight %) using the following formula.

y = 142.7-2.513.X The monomer ratio during polymerization for copolymerization within the above range varies depending on polymerization conditions such as polymerization temperature, but orthochlorophenylmaleimide is 0.2 to 36 It is about % by weight.

The copolymer used in the present invention preferably has a degree of polymerization of about 300 to 3,000 as determined by the method of JIS K-6721, and when a molded article is obtained by an extruder, the degree of polymerization is about 500.
-2000 is more preferable, and 500-150
Most preferably, it is 0. If the degree of polymerization is less than 300, it will not be possible to obtain a molded product with a strength sufficient for practical use, and if it is greater than 3000, the molding process will be extremely difficult, making it unsuitable for practical use.

The degree of polymerization of the copolymer was measured as follows.

Approximately 5 g of the copolymer of the present invention is dissolved in 250 cc of tetrahydrofuran, and the solution is centrifuged to remove the precipitate. Menol 41 is gradually added dropwise to the solution to reprecipitate the copolymer. The reprecipitate is filtered and dried in a vacuum dryer to provide a sample for measuring the degree of polymerization. The degree of polymerization of the sample was determined by the method of JIS K6721.

The stabilizer used in the present invention may be any known stabilizer, such as lead white, tribasic lead sulfate, dibasic lead phosphite, dibasic lead phthalate, tribasic maleic acid. Lead, lead salt stabilizers such as lead silicate and its silica gel co-precipitate, metal soaps such as magnesium soap, calcium soap, barium soap, cadmium soap, zinc soap, lead soap, tin soap, cadmium-barium type, cadmium - Liquid stabilizers such as barium-zinc type and barium-zinc type, organotin stabilizers such as tin alkyl sulfur compounds, tin aryl sulfur compounds, tin alkyl oxygen compounds, tin aryl oxygen compounds, organotin carboxylic acids, and organotin mercaptides. agent,
Glycidyl ethers and epoxy resins, epoxidized fats and oils and epoxidized natural oil acids and alkyl esters of resin acids, epoxy stabilizers such as epoxy derivatives of cyclohexane, organic phosphorous compounds such as trialkyl phosphites, triphenyl phosphites, Examples include polyhydric alcohols and amine compounds.

Lead salt stabilizers, metal soaps, etc. that are not liquid at room temperature are preferred, but liquid stabilizers can also be used as long as the amount of additives that are liquid at room temperature is 5% by weight or less of the entire composition.

Examples of lubricants include metal soaps such as magnesium stearate, calcium stearate, barium stearate, zinc stearate, and lead stearate, liquid paraffin, natural paraffin, polyethylene wax, hydrocarbons such as chlorinated hydrocarbons and fluorocarbons, and stearin. acids, fatty acids such as hehenic acid, alaxic acid, oxyfatty acid, fatty acid amides, fatty acid amides such as alkylene bis fatty acid amide, fatty acid lower alcohol esters,
Fatty acid esters such as polyglycol esters of fatty acids, fatty alcohol esters of fatty acids, polyhydric alcohols,
Examples include polyglycol, polyglycerol, partial esters of fatty acids and polyhydric alcohols, partial esters of fatty acids and polyglycols, and partial esters of fatty acids and polyglycerols.

These lubricants are preferably ones that are not liquefied at room temperature, but like the stabilizers, liquid ones can also be used by making sure that the additives that are liquefied at room temperature account for less than 5% of the total composition. be.

Examples of fillers include calcium carbonate, clay, hydrated silicic acid, anhydrous silicic acid, calcium silicate, aluminum silicate, asbestos, antimony oxide, talc, aluminum trihydrate, hydrated zinc borate, magnesia, baking soda, and nitric acid. processing,
Examples include calcium hydroxide, mica, and synthetic fluorinated mica.

Examples of colorants include organic pigments such as azo lake,
Azo pigments such as insoluble ab and condensed azo, phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, vat dye pigments such as anthraquinone, perylene, thioindico, and isoindoline, basic dye lakes, and acid dyes. Examples include dyeing lake pigments such as lake, quinacridone pigments, dioxazine pigments, etc. Inorganic pigments include precipitated pigments such as chromates, molybdates, oxides, cyanides, oxides, sulfides, etc. Examples include precipitated fired pigments, oxide pigments, fired pigments such as ultramarine blue and cobalt blue, metal powders, pearl pigments, etc.

As a plasticizer, for example, dibutyl phthalate (DBP
), di-2-ethylhexyl phthalate (DOP)
, di-n-octyl phthalate (n-DOP), butyl lauryl phthalate (BLP), dilauryl phthalate (D L P ), butyl benzyl phthalate (BB
Phthalate esters such as P), linear dibasic acid esters such as dioctyl adipate (Do8), dioctyl azelate (DOZ), dioctyl sebacate (DO5), tricresyl phosphate (TCP), phosphate (TXP), monooctyl diphenyl phosphate, 1000 butyl dixylenyl phosphate, trioctyl phosphate (TOP), methyl acetyl lysyllate, butylacetyl lysyllate, methyl cellosolve lysyllate, etc. Castor oil derivatives, epoxidized vegetable oils, tetraethylene glycol esters, ethylene glycol derivatives such as butylphthalyl butyl glycolate, polyester plasticizers, chlorinated paraffins, chlorinated products such as butyl stearate pentachloride, petroleum-based higher aromatic compounds Examples include petroleum auxiliary plasticizers such as nitrile-based synthetic rubber.

Polyester plasticizers that are not liquid at room temperature are preferred, but liquid plasticizers can also be used as long as the additives that are liquid at room temperature account for 5% by weight or less of the total composition.

Examples of other resins include vinyl chloride resins and known resins that can be mixed with vinyl chloride resins, such as ABS resins, MBS resins, and urethane resins.

The heat-resistant polyvinyl chloride resin composition of the present invention may contain additives that are liquid at room temperature at a content of 5% by weight or less, preferably 3% by weight or less, and further 1% by weight or less based on the total composition.
It is preferably less than % by weight.

If the amount of the additive, which is liquid at room temperature, exceeds 5% by weight of the entire composition, the Piccad softening point will be significantly lowered and the additive cannot be used.

As a method for molding the heat-resistant polyvinyl chloride resin composition of the present invention, a conventional molding method for vinyl chloride resin can be applied as is.

〔Example〕

The present invention will be explained below using examples.

The Piccad softening point is measured according to JIS K-7206.
A load of 1 kgf was used according to the method of .

Example 1 Internal volume 800! 310 kg of water, 70% t-
Butyl peroxyneodecanate solution 100g, 75
%3゜5.5-trimethylhexanoyl peroxide 74g and orthochlorophenylmaleimide 14kg
After degassing under reduced pressure, 16.6 kg of a 5% aqueous solution of partially saponified polyvinyl alcohol with a degree of polymerization of about 2000 and a degree of saponification of 80 mol% was added, and then 1 mol of vinyl chloride monomer was added.
49 kg was charged, the temperature was raised to 64.5°C, the reaction was carried out, and the reaction was stopped at a gauge pressure of 7 kg/cffl. After dehydration and drying, 127 kg of resin was obtained. The orthochlorophenylmaleimide monomer unit in this resin is 10% by weight,
The degree of polymerization was 660.

A molded product of a composition obtained using this resin by the method described below had a Vicat softening point of 108°C.

The sample piece was prepared in the following manner.

Weigh resin, tribasic lead sulfate, dibasic lead phosphite, lead stearate, and calcium stearate in the proportions shown in Table 1 into a stainless beaker, mix thoroughly with a spatula, and then heat to 160°C with a milling roll. The mixture was kneaded for 10 minutes, further heated at 180°C for 3 minutes, and then pressed for 5 minutes to obtain a pressed sheet with a thickness of 3 mm.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that orthochlorophenylmaleimide was not used.
15 kg of resin was obtained. If the orthochlorophenylmaleimide monomer unit in this resin is 0% by weight, the degree of polymerization is 81.
It was 0. Furthermore, the Vicat softening point of the molded product prepared in the same manner as in Example 1 was 88.6°C.

Examples 2 to 10, Comparative Examples 2 to 5 Sample pieces were prepared using the formulations shown in Table 2 in the same manner as in Example 1, and the Vicat softening points were measured. The results are shown in Table 2.

Example 11 Orthochlorophenylmaleimide monomer unit content 3.8
Vinyl chloride copolymer 100 with a degree of polymerization of 740 in weight%
1 part of tribasic lead sulfate, 1 part of dibasic lead stearate, and 2 parts of lead stearate were mixed in a Henschel type mixer and the triblend powder was pelletized at 165°C using a 40 mmφ single screw extruder. to produce a pellet-like composition. The composition was heated at 170° in a 40 mmφ single screw extruder.
A heald-shaped molded product with a width of 25 mm and a thickness of 3.5 mm was extruded at C and the Vicat softening point was measured, and the Vicat softening point was 93°C.

〔Effect of the invention〕

The heat-resistant polyvinyl chloride resin composition of the present invention has improved heat resistance, particularly Piccad softening temperature, and is extremely useful as a heat-resistant polyvinyl chloride resin composition.

Claims (1)

[Claims] 1. Orthochlorophenylmaleimide monomer unit 0.
The additive composition consists of 60% by weight or more of an orthochlorophenylmaleimide-vinyl chloride copolymer containing 2 to 40% by weight and (b) 40% by weight or less of an additive containing at least a stabilizer, and which is liquid at room temperature. A heat-resistant polyvinyl chloride resin composition whose content is 5% by weight or less based on the total weight of the composition. 2. The heat-resistant polyvinyl chloride resin composition according to claim 1, wherein component (a) has a degree of polymerization of 300 to 3,000.