JPH02202940A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To provide the title resin composition excellent in moldability and giving a molding excellent in appearance, heat resistance, colorability, etc., by mixing a specified vinyl chloride/maleimide copolymer with a specified chlorinated polyvinyl chloride and a stabilizer in a specified mixing ratio. CONSTITUTION:A vinyl chloride/maleimide copolymer of an average degree of polymerization of 700-2000, comprising 50-95wt.% structural units (A) derived from vinyl chloride, 50-5wt.% structural units (B) derived from an N-substituted maleimide compound of the formula (wherein R<1> is a 1-30C substituted or unsubstituted aliphatic, alicyclic or aromatic hydrocarbon group; R<2> and R<3> are each H, F, Cl, Br, CN or a 3C or lower alkyl), e.g. N-methylmaleimide, is prepared. A vinyl chloride resin composition is produced by mixing 100 pts.wt. this copolymer with 5-50 pts.wt. chlorinated polyvinyl chloride obtained by post-chlorinating a polyvinyl chloride of an average degree of polymerization of 400-2000 and an effective amount of an organotin or/and lead stabilizer.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a vinyl chloride resin composition useful as plastic molded products that are widely used in various industrial fields, particularly those with heat deformation resistance, colorability, and moldability. This invention relates to a vinyl chloride resin composition with excellent processability.

(Issues to be solved by the prior art and the invention)> It is known that the heat deformation resistance of vinyl chloride-based resins is inferior to polyvinyl chloride, but good to post-chlorinated vinyl chloride. Vinyl chloride has disadvantages such as poor colorability, generation of acidic gas during processing which corrodes equipment, and poor moldability, especially compared to polyvinyl chloride.

Therefore, vinyl chloride monomer and N-
The present invention aims to provide a novel vinyl chloride resin composition from which substituted maleimide compound processed products can be obtained.

(Means for solving commercial problems) The vinyl chloride resin composition according to the present invention is as follows.

(1) 50 to 95% by weight of structural units derived from vinyl chloride
♂ (wherein, R1 is a substituted or unsubstituted aliphatic, alicyclic, or aromatic hydrocarbon group having 1 to 30 carbon atoms, R1
and R3 are the same or different from each other, hydrogen, fluorine,
A vinyl chloride-N-substituted maleimide resin composition based on a copolymer consisting of a chlorine or bromine atom, a cyano group, or an alkyl group having 3 or less carbon atoms has been proposed. Although it is superior to post-chlorinated vinyl chloride in processability, it is slightly inferior in heat resistance, and it is inferior to polyvinyl chloride in processability and thermal stability.

Therefore, the object of the present invention is to improve this vinyl chloride-N-substituted maleimide resin composition, and to improve the molding ♂ which has good heat deformation resistance, molding processability, and excellent colorability (wherein R1 is 1 carbon atom ~30 substituted or unsubstituted aliphatic, cycloaliphatic, or aromatic hydrocarbon groups %R2
and R3 are the same or different from each other, hydrogen, fluorine,
Atom of chlorine or bromine.

an average degree of polymerization of 700 to z containing 5 to 50% by weight of structural units derived from an N-substituted maleimide compound represented by a cyano group or an alkyl group having 3 or less carbon atoms.
, ooo vinyl chloride-maleimide copolymer 100 parts by weight, (2) chlorinated polyvinyl chloride obtained by post-chlorinating polyvinyl chloride with an average degree of polymerization of 400-2,000 5-50
parts by weight, and (3) an effective amount of at least one stabilizer selected from organotin stabilizers and lead stabilizers.

The present invention will be explained in detail below.

The vinyl chloride-maleimide copolymer used as component (1) in the composition of the present invention is obtained from a vinyl chloride monomer and an N-substituted maleimide compound represented by the above general formula. Specific examples of the N-1-substituted maleimide compounds that can be used include N-methylmaleimide, N-ethylmaleimide, N-n-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, and N-methylmaleimide.

t-Butylmaleimide, N-hexylmaleimide, N-
Cyclohexylmaleimide, N-phenylmaleimide,
N-hydroxyphenylmaleimide, N-(p, m, o
)-Hydroxyphenylmaleimide, N-(ppn't
to)-methoxyphenylmaleimide, N-(p+m*
o)-Chlorophenylmaleimide, N-(ptm,o)
-carboxyphenylmaleimide, N-(p.

m,o)-nitrophenylmaleimide, N-laurylmaleimide, N-bicyclo-(2,2,1)-hebutane-
Examples include 1-yl-3-methylmaleimide, N-9,LO-ethano-9,10-dihydroanthracen-2-ylmaleimide, N-triphenylmethylbenzylmaleimide, among which R is methyl,
t-Butyl, cyclohexyl, bicyclo-(2°2.1
)-hebutan-1-yl-3-methyl, 9,10-ethano-9,10-dihydroanthracenyl, triphenylmethylbenzyl and the like are particularly preferred.

The vinyl chloride-maleimide copolymer composed of this vinyl chloride monomer and the above N-substituted 71 neuimide compound contains 50 to 95% by weight of constitutional units derived from the vinyl chloride monomer,
It is preferably 70 to 90% by weight, and it is necessary that the constituent units derived from the N-substituted maleimide compound account for 5 to 50% by weight, preferably 10 to 30% by weight. If the content of the structural unit derived from the N-substituted maleimide compound is less than 5% by weight, the heat resistance of the copolymer will not be sufficiently improved, and if it exceeds 50% by weight, the melting temperature of the copolymer will be too high, making it difficult to process. make sex worse.

In addition, in the production of this copolymer, if necessary, other polymerizable monomers and at least one polymer that can be graft-polymerized with vinyl chloride are added, and the structural units derived from these are added to the resulting copolymer. It can be used in amounts such that in the coalescence it is less than 30% by weight, preferably less than 15% by weight. If it exceeds 30% by weight, it is not preferable because the inherent properties of vinyl chloride resin, such as mechanical strength and durability, are lost.

Other polymerizable monomers used here include:

Vinyl acetate, vinyl propionate, vinyl caproate,
Vinyl esters such as vinyl laurate and vinyl stearate; olefins such as ethylene, propylene, and imbutylene; alkyl vinyl ethers such as isobutyl vinyl ether, octyl vinyl ether, dodecyl vinyl ether, and phenyl vinyl ether; vinylidene chloride, vinyl fluoride, and propylene chloride , halogenated olefins such as vinyl bromide; acrylic acid and methacrylic acid esters such as ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, etc. ; Acrylic derivatives such as acrylic acid, methacrylic acid, crotonic acid, acrylonitrile, maleic anhydride, and itaconic anhydride; etc., and these can be used alone or in combination of two or more.

Polymers that can be graft-polymerized with vinyl chloride include: ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer, chlorinated polyethylene, polyurethane, polybutadiene-styrene-methyl methacrylate-h ( MBS), polybutadiene-acrylonitrile-(α-methyl)styrene (ABS), polybutyl acrylate, butyl rubber, polystyrene, styrene-butadiene copolymer, crosslinked acrylic rubber, and the like.

The production of this vinyl chloride-maleimide copolymer involves heating the above components at 20-80°C in the presence of a free radical-generating catalyst.
This can be carried out by any one of bulk polymerization, suspension polymerization, emulsion polymerization, etc. However, it is industrially and economically advantageous to use suspension polymerization in the membrane.

The free radical generating catalyst may be one conventionally used for vinyl chloride polymerization, such as decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl Barcarbonate compounds such as peroxydicarbonate, jetoxyethyl peroxydicarbonate; t-butyl peroxybiparate, t-hexylveroxypiparate, t-
Perester compounds such as butylperoxyneodecanate and α-cumylperoxyneodecanate; acetylcyclohexylsulfonyl peroxide, 2,4.4-
Trimethylbenzene-2-peroxyphenoxyacetate, 3. Peroxides such as 5,5-trimedelhexanoyl peroxide; α,α′-azobisisobutyronitrile, α,αゝ-azobis-2,4-dimethylvaleronitrile, α,α2-azobis(4 -methoxy-2,4
-dimethylvaleronitrile), potassium persulfate, ammonium persulfate, hydrogen peroxide, etc., and these can be used alone or in combination of two or more.

In addition, in the suspension polymerization, commonly used dispersion aids 1 such as methyl cellulose, ethyl cellulose,
Water-soluble cellulose ethers such as hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and carboxymethylcellulose; synthetic polymers such as fully or partially saponified polyvinyl alcohol, acrylic acid polymers, polyvinylpyrrolidone, and 71-twinic anhydride-vinyl acetate copolymer; Compounds; Natural polymeric substances such as starch and gelatin; Oil-soluble emulsifiers such as sorbitan monolaurate, sorbitan triolate, glycerin tristearate, and ethylene oxide brobylene oxide block copolymer; Polyoxyethylene sorbitan monolaurate, polyoxyethylene Water-soluble emulsifiers such as glycerin oleate and sodium laurate may be used alone or in combination of two or more.

Furthermore, in this polymerization system, polymerization degree regulators, chain transfer agents, pH regulators, gelling improvers, antistatic agents, antioxidants, and scale inhibitors used as appropriate for vinyl chloride polymerization are included. It is also optional to add.

The other conditions for this polymerization and the method of charging the aqueous medium, vinyl chloride monomer, other comonomers, dispersion aids, polymerization initiator, etc. to the polymerization vessel can be carried out in the same manner as conventional methods. The polymerization conditions, such as the charging ratio of 1 and the degree of polymerization, may also be the same.

The vinyl chloride-maleimide copolymer thus obtained is required to have an average degree of polymerization of 700 to 2,000, but if it is less than 700, the impact resistance will decrease and Exceeding this is not preferable because processability will be markedly deteriorated and it will be economically disadvantageous.

The chlorinated polyvinyl chloride used as component (2) in the composition of the present invention has an average degree of polymerization of 400 to 2.0.
00, preferably? Post-chlorinated polyvinyl chloride of 00 to i, ooo is used. If the average degree of polymerization of polyvinyl chloride is less than 400, the mechanical strength such as impact resistance of the resulting vinyl chloride resin composition will decrease, and if it exceeds 2,000, the melt viscosity will increase.
Molding processability is significantly reduced.

On the other hand, the chlorine content of this chlorinated polyvinyl chloride is 60~
It is preferably 80% by weight, particularly 60 to 70% by weight. If the chlorine content is less than 60% by weight, the heat resistance of the composition will decrease, and if it exceeds 80% by weight, the processability will be significantly decreased, which is not preferred.

The method for producing chlorinated polyvinyl chloride used here includes, for example, suspending polyvinyl chloride having the above average degree of polymerization in an aqueous medium containing a solvent such as chloroform or an aqueous medium containing no solvent. There is a method of chlorinating with a photocatalyst, or a method of chlorinating with a gas phase flow method in the presence of a photocatalyst or a peroxide catalyst.

In addition to chlorinated vinyl chloride homopolymers, this chlorinated polyvinyl chloride includes vinyl chloride-ethylene copolymers, vinyl chloride-vinyl acetate copolymers, and vinyl chloride-vinylidene chloride copolymers. It also contains a composition obtained by chlorinating a chlorinated vinyl chloride copolymer or a mixture thereof.

By incorporating this chlorinated polyvinyl chloride into the vinyl chloride resin composition according to the present invention, the appearance thereof is not impaired and the excellent properties provided by the vinyl chloride-maleimide copolymer are not impaired. , heat resistance, initial colorability, and especially moldability.

In this resin composition, the blending ratio of the vinyl chloride-maleimide copolymer used as component (1) and the chlorinated polyvinyl chloride is 5 to 5 parts by weight per 100 parts by weight of the copolymer. It is 50 parts by weight, preferably 20 to 45 parts by weight. If the proportion of chlorinated polyvinyl chloride used is less than this range, the resulting resin composition may have insufficient heat resistance, and if it is greater than this range, sufficient effects commensurate with the amount used may not be obtained. This is not preferable because it becomes uneconomical and the molding processability is significantly reduced, impairing the versatility of the resin composition.

Regarding the organotin-based stabilizer or lead-based stabilizer used as component (3) in the composition of the present invention, the former will be explained first. Di-n-alkyltin dilaurate, dibutyltin dimaleate, dibutyltin lauryl mercaptide, dioctyltin-s, s
'-bis-(isooctyl-mercaptoacetate),
Examples include dibutyltin bis-isooctylthioglycolate, di(n-octyl)tin maleinate polymer, dibutyltin mercaptopropionate, and the like. Among these, dimethyltin mercaptide and a combination of dimethyltin mercaptide and dibutyltin dimaleate are preferred.

Examples of the latter lead-based stabilizers include tribasic sulfates,
Organic and inorganic leads such as dibasic lead phosphite, dibasic lead phosphite sulfite, basic lead sulfite, dibasic lead phthalate, dibasic lead stearate, stearate, silica gel co-precipitated lead silicate, etc. Examples include compounds.

These organotin-based and lead-based stabilizers may be used alone or in combination of two or more, *
In addition, the amount of these stabilizers used is the same as that used in ordinary vinyl chloride resins, and is an effective amount to achieve the purpose, but more specifically, (1) chloride as a component 0.0% per 100 parts by weight of vinyl-maleimide copolymer.
It is preferably 5 parts by weight or more, particularly 1 to 20 parts by weight. If the amount is too small, the effects of the present invention will be difficult to exhibit, while if it is too large, the heat deformation resistance may be impaired.

In addition to the components (1) to (3), the composition of the present invention also includes:
Various components can be blended as needed.

For example, when applying this to fields that require mechanical strength, the average degree of polymerization of components other than the vinyl chloride-maleimide copolymer (1) is
A certain amount of vinyl chloride resin can be used in combination. Examples of vinyl chloride resins include, in addition to vinyl chloride homopolymers, copolymers of vinyl chloride and ethylene, propylene, etc., ethylene-vinyl acetate copolymers, and ethylene-vinyl acetate copolymers.
Examples include ethyl acrylate copolymers, multicomponent copolymers obtained by graft copolymerizing vinyl chloride onto ethylene copolymers such as chlorinated polyethylene, and blends of two or more of these.

In addition, from the viewpoint of processability of the composition and physical properties required for molded objects, lubricants, processing aids, antistatic agents, fillers, antioxidants, flame retardants, ultraviolet absorbers, colorants, and modifiers 1 smoke suppression. Agents and the like may also be added within a range that does not impair the effects of the present invention.

Examples of lubricants that can be applied for this purpose include:

Magnesium such as lauric acid, stearic acid, oleic acid, ethylhexoic acid, ricinoleic acid, naphthenic acid, etc.
Metal salts such as aluminum, calcium, cadmium, lead, barium, and lithium; organic tin fatty acid salts; fatty acids and their esters; amides; higher ketones; higher alcohols; paraffin wax; polyethylene wax; acrylic wax; natural wax silicone, etc. Although it can be mentioned,
Among these, metal soaps are not preferred in terms of thermal stability, while monoglycerides of fatty acids such as stearic acid are preferred because they do not adversely affect thermal stability.

Processing aids include acrylonitrile-styrene copolymer (AS), methyl methacrylate-styrene copolymer (MS), acrylonitrile-butadiene-styrene copolymer (ABS), and methyl methacrylate-butadiene-styrene copolymer (MBS). ), Pararoid.

Examples include epichlorohydrin, polymethacrylate, polybutadiene, polystyrene, polyethylene, acrylate polymers, and ethylene-vinyl acetate copolymers.

As the antistatic agent, various cationic, anionic, nonionic, or amphoteric surfactants are used.

In addition, heat resistance improvers such as acrylonitrile-α-methylstyrene-butadiene copolymer and PMMA and acrylic acid ester copolymer can be mentioned.

(Examples) Hereinafter, specific aspects of the present invention will be explained using Examples and Comparative Examples, but the present invention is not limited to these Examples.

Examples 1 to 9 and Comparative Examples 1 to 4 As the vinyl chloride-maleimide copolymer in each example, copolymers I to ■ containing N-substituted maleimide components of the type and amount shown in Table 1 were used, The following chlorinated polyvinyl chloride was used.

i: HA-31K (manufactured by Tokuyama Tanemizu Kogyo ■, chlorine content 68
%)it: HA-51K(nn
67#)iii:I(A-15E(# #
62#) Further, as the vinyl chloride polymer as an additional component, T K-1000 (manufactured by Shin-Etsu Chemical Co., Ltd., average degree of polymerization 1050) was used.

Table 1 To these vinyl chloride copolymers, chlorinated polyvinyl chloride, and vinyl chloride polymers as additional components, stabilizers, metal soaps, lubricants, and other additives were added in the proportions shown in Table 2, and Examples were prepared. Resin compositions of Examples 1 to 9 and Comparative Examples 1 to 4 were prepared.

Each of the obtained resin compositions was kneaded for 5 minutes using a 6-inch diameter hot roll heated to a surface temperature of 200°C, and the roll suitability at the time of cross-wiring was determined by the windability on the roll and the surface smoothness of the obtained sheet. Comprehensive evaluation was made based on the following criteria. After kneading, it is made into a sheet, and then pressed using a flat plate press for 200
A test piece was prepared by press molding at a temperature of 180 kg/d for 8 minutes. The yellowness index (YI) of this was measured according to JIS-7105, and this value was evaluated as coloring property according to the following criteria. Also, using this, VICAT
The penetration temperature was measured by a method according to JIS K-7206A method, and the results are also listed in Table 2.

・Roll suitability judgment criteria: Wrapping time Smoothness within 1 minute Excellent 2# Good 3 Fairly bad 3# or more Significant unevenness ・Colorability judgment criteria: YI value 50 or less 50-75 75-100 100 or more Roll suitability judgment・・・・・・・・・O ・・・・・・・・・0 ・・・・・・・・・Δ ・・・・・・・・・X Colorability judgment・・・・・・・・・・・・O ・・・・・・・・・0 ・・・・・・・・・Δ ・・・・・・・・・X The appearance of the test piece made of the resin composition of the present invention is As shown in Table 2, other test measurements also showed good results, but all of the resin compositions as comparative examples had inferior results.

(Effects of the Invention) The vinyl chloride resin composition of the present invention has excellent appearance, heat resistance, moldability, etc., and is therefore widely used in the fields of plastic products such as industrial and building materials.

Claims (1)

[Claims] 1. (1) 50 to 95% by weight of structural units derived from vinyl chloride and general formula: ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 is the number of carbon atoms from 1 to 30 substituted or unsubstituted aliphatic, cycloaliphatic, or aromatic hydrocarbon groups, R
^2 and R^3 are the same or different from each other and are hydrogen, fluorine, chlorine or bromine atoms, cyano groups, or alkyl groups having 3 or less carbon atoms) A structural unit derived from an N-substituted maleimide compound (2) 100 parts by weight of a vinyl chloride-maleimide copolymer with an average degree of polymerization of 700 to 2,000 containing 5 to 50% by weight; Chlorinated polyvinyl chloride 5-50
parts by weight, and (3) an effective amount of at least one stabilizer selected from organotin stabilizers and lead stabilizers. 2. The vinyl chloride resin composition according to claim 1, wherein the chlorinated polyvinyl chloride contains 60 to 80% by weight of chlorine.