JPS63251446A - 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, and colorability, by mixing a vinyl chloride/N-chclohexylmaleimide copolymer with additives containing a stabilizer. CONSTITUTION:This resin composition comprises at least 60wt.% vinyl chloride/ N-cyclohexylmaleimide copolymer (a) containing 0.2-40wt.% N-cyclo hexylmaleimide monomer units and at most 40wt.% additives (b) containing at least a stabilizer, wherein the amount of additives which are liquid at normal temperature is at most 5wt.%, based on the total composition. It is preferable 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 with an improved degree of coloration.

[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, and for example, JP-A-57-162745 [Polyblend Composition], JP-A-57-61040 [Vinyl Chloride Resin Composition], etc. 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. Further, a copolymer of orthochlorophenylmaleimide and vinyl chloride solves the above-mentioned drawbacks, but unfortunately it has the disadvantage of being highly colored and having major practical limitations.

[Means for Solving the Problems] The present inventors have conducted extensive research to solve the above-mentioned problems, and have completed the present invention.

That is, the heat-resistant polyvinyl chloride resin m-acid of the present invention comprises (a) 60% by weight of a vinyl chloride-N-cyclohexylmaleimide copolymer containing 0.2 to 40% by weight of N-cyclohexylmaleimide monomer units; In addition to the above, (b) the composition is characterized in that it comprises 40% by weight or less of an additive containing at least a stabilizer, and that the additive, which 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 coelectrifying N-cyclohexylmaleimide 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 with improved coloration of the present invention contains 60% by weight or more of a vinyl chloride copolymer containing 0.2 to 40% by weight of N-cyclohexylmaleimide monomer units. It must contain at least a stabilizer, and if necessary, a lubricant, filler, and other additives, such as colorants, plasticizers, and other resins, within a range not exceeding 40% by weight. However, it is necessary that the additive, which is liquid at room temperature, accounts for 5% by weight or less of the entire composition.

In the above-mentioned heat-resistant polyvinyl chloride resin composition with improved coloring degree, it is more preferable that the vinyl chloride copolymer is 70% by weight or more and the other components are 30% by weight or less, and further 80% by weight or more, respectively. It is preferably 20% by weight or less. 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 N-cyclohexylmaleimide monomer unit in the vinyl chloride copolymer is preferably 0.2 to 40% by weight, and 0.5 to 40% by weight.
30% by weight is more preferred, and 1 to 30% by weight is most preferred. If it is less than 0.2% by weight, the improvement in the Vicat softening point will be negligibly small, and if it is more than 40% by weight, the processability will deteriorate, which is not preferable.

The amount of N-cyclohexylmaleimide monomer units (y, weight %) in the copolymer is determined by the elemental analysis value of chlorine (X, weight %).
), using the following formula.

y = 100.0 - 1.761 x .2-3
It is about 6% by weight.

The copolymer of the present invention 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 according to JIS-6121 method.

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
0 is most preferred. 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 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 oils and fats and epoxidized natural fatty acids and alkyl esters of resin acids, epoxy stabilizers such as epoxy derivatives of cyclohexane, organic phosphoric acid compounds such as trialkyl phosphites, triphenyl phosphites, etc. , polyhydric alcohols, amine compounds, etc.

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 behenic acid, araxic acid, oxyfatty acids, fatty acid amides, alkylene bis fatty acid amidothyls, fatty acid esters such as polyglycol esters of fatty acids, fatty alcohol esters of fatty acids, polyhydric alcohols, polyglycols, polyglycerols, fatty acids and Examples include partial esters of 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 if the additives that are liquefied at room temperature account for 5% by weight or less of the total composition. .

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 azo 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),
Phthalate esters such as di-n-octyl phthalate (n-DOP), butyl lauryl phthalate (BLP), dilauryl phthalate (DLP), butylbenzyl fucrate (BBP), dioctyl adipate (DOA)
), dioctylasedi) (DOZ), linear dibasic acid esters such as dioctylsepacate (005), tricresyl phosphate (TCP), ) dixylenyl phosphate (TXP), monooctyl diphenyl phosphate , monobutyl dixylenyl phosphate, phosphoric acid esters such as trioctyl phosphate (TOP), castor oil derivatives such as methyl acetyl lysyllate, butyl acetyl lysyllate, methyl cellosolve lysyllate, epoxidized vegetable oil, tetraethylene glycol ester , ethylene glycol derivatives such as butylphthalyl butyl glycolate, polyester plasticizers, chlorinated paraffins, chlorinated products such as pentachlorinated butyl stearate, petroleum auxiliary plasticizers such as petroleum-based higher aromatic series, nitrile synthetic rubber, etc. can be mentioned.

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 with improved coloration of the present invention may contain an additive that is liquid at room temperature in an amount of 5% by weight or less, and 3% by weight or less of the entire composition. is preferable, and more preferably 1% by weight or less.

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

As a method for molding the heat-resistant polyvinyl chloride resin composition with improved degree of coloration 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 pinkado softening point was measured using a load of 1 kgf according to the method of JIS K-7206.

The 8E of the pressed sheet or molded product was measured using a digital colorimetric color difference calculator manufactured by Suga Shikenki ■ using a standard white plate standard, and this was used as a measure of the degree of coloration.

Example 1 310 kg of water and 70% t were added to a polymerization machine with an internal volume of Boo f2.
-butyl peroxyneodecanate solution 100g, 75
%3゜5.5-trimethylhexanoyl peroxide 75g and N-cyclohexylmaleimide 4,9
kg of partially saponified polyvinyl alcohol with a degree of polymerization of about 2000 and a degree of saponification of 80 mol%.
% aqueous solution, then 149 kg of vinyl chloride monomer were charged, the temperature was raised to 64.5°C to react, and the reaction was stopped at a gauge pressure of 7 kg/cJ. After dehydration and drying, 119 kg of resin was obtained. The N-cyclohexylmaleimide monomer unit of this resin was 3.9% by weight, and the degree of polymerization was 770.

A molded product of the composition produced using this resin by the method described below had a Vicat softening point of 92.8° C1 and a coloring degree ΔE of 19.

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. Knead for 10 minutes at
After heating at 0°C for 3 minutes, press for 5 minutes to a thickness of 3m.
A press sheet of m was obtained.

Table 1 Vicat Softening Point Measurement Comparative Formulation Example 1 Polymerization was carried out in the same manner as in Example 1 except that N-cyclohexylmaleimide was not used in Example 1. 115 kg
products were obtained. The N-cyclohexylmaleimide monomer unit in the product was 0% by weight, the degree of polymerization was 810, and the Vicat softening points of the molded product obtained in the same manner as in Example 1 were 8 days and 6 days.
The degree of coloration at °C1 was 8E.

Comparative Example 2 Polymerization degree 740, orthochlorophenylmaleimide content 13
．． When sample pieces were prepared from 8% orthochlorophenylmaleimide-vinyl chloride copolymer using the same method as in Example 1 and the formulation shown in Table 1, the Vicat softening point was 93.5°C and the degree of coloration ΔE was 27. Met.

Examples 2 to 5, Comparative Examples 3 to 5 Sample pieces were prepared using the formulation shown in Table 2 in the same manner as in Example 1, and the Vicat softening point and degree of coloration ΔE were measured.

The results are shown in Table 2 together with Example 1 and Comparative Example 1.2.

The copolymer of the present invention has a Vicat softening point and a coloration degree Δ
E has been improved.

Example 6 N-cyclohexylmaleimide monomer unit 3.9% by weight
100 parts of N-cyclohexylmaleimide-vinyl chloride copolymer with a degree of polymerization of 770, 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. 40 blended powder
The mixture was pelletized at 165°C using a mmφ single-screw extruder to produce a pelletized composition. The composition was heated to a width of 25 mm and a thickness of 3.5 mm at 170°C using a 40 mmφ single screw extruder.
A belt-shaped molded product was extruded. Vicat softening point is 92,
2°C1 coloring degree 8E was 7.

Examples 7 to 11, Comparative Examples 6 to 7 Molded products were extruded using the same method as in Example 6 and the formulation shown in Table 3. The copolymer of the present invention has improved Vicat softening point and coloring degree ΔE [Effects of the invention] The heat-resistant polyvinyl chloride resin composition of the present invention with improved coloring degree has high heat resistance, especially Piccad softening temperature. In addition, the degree of coloration, especially 8E, is small, making it extremely useful as a heat-resistant polyvinyl chloride resin composition with improved degree of coloration.

Claims (1)

[Scope of Claims] 1. (a) 60% by weight or more of a vinyl chloride-N-cyclohexylmaleimide copolymer containing 0.2 to 40% by weight of N-cyclohexylmaleimide monomer units; and (b) at least a stabilizer. 1. A heat-resistant polyvinyl chloride resin composition with an improved degree of coloring, which comprises 40% by weight or less of additives including: 2. A heat-resistant polyvinyl chloride resin composition with an improved degree of coloring according to claim 1, wherein component (a) has a degree of polymerization of 300 to 3,000.