JP3079169B2 - Hard vinyl chloride resin composition - Google Patents

Description

The present invention relates to a stabilized hard vinyl chloride resin composition, and more particularly, to a metal salt or a basic metal salt of titanium dioxide and an alkyl phosphoric acid. The present invention relates to a hard vinyl chloride resin composition which is stabilized by being added.

[Conventional technology and problems]

Vinyl chloride resin is inexpensive, and has features such as excellent weather resistance, moldability, and gas barrier properties.
Conventionally, films, sheets, and various molded products have been widely used.However, when performing heat processing, it is easy to cause thermal decomposition mainly due to dehydrochlorination, and as a result, the mechanical properties of processed products deteriorate, The color tone deteriorates, resulting in significant disadvantages. In order to avoid such disadvantages, it is necessary to add one or several kinds of heat stabilizers to the vinyl chloride resin to suppress deterioration in the processing step.

Conventionally, various organic acid metal salts, organic tin compounds and the like have been used for such purpose. As a result, almost satisfactory results were obtained in terms of thermal stability.

However, at the present time when high-speed processing equipment is demanded, the processing temperature is inevitably increased, and further improvement in thermal stability at high temperatures is desired.

In addition, it is not practically sufficient in the case of molding, and if the example is taken by the calender roll method, a plate-out phenomenon occurs on the calender roll surface, impairing the shape of the surface of the molded product, and significantly lowering the processing efficiency. In particular, when titanium dioxide is used, an additive that easily causes a plate-out phenomenon, has excellent thermal stability at high temperatures, and does not cause plate-out has been desired.

[Means for solving the problem]

The present inventors have conducted intensive studies in order to improve plate-out which is a drawback of the hard vinyl chloride resin blended with titanium dioxide, and as a result, a divalent or trivalent metal salt or base of a specific alkyl phosphoric acid has been obtained. The present inventors have found that plateout can be significantly reduced by adding a neutral metal salt, and have reached the present invention.

That is, according to the present invention, trivalent or trivalent of 1 to 30 parts by weight of titanium dioxide and an alkyl phosphoric acid selected from the following general formulas (I) and (II) based on 100 parts by weight of a hard vinyl chloride resin. The present invention provides a hard vinyl chloride resin composition obtained by adding 0.01 to 10 parts by weight of a metal salt or a basic metal salt of

(In the formula, R represents an optionally substituted alkyl group having 6 to 30 carbon atoms.) Hereinafter, the present invention having the above gist will be described in more detail.

The titanium dioxide used in the present invention may be either a rutile type or an anatase type, and a commercially available titanium dioxide compound can be used as it is.
Moreover, the thing which processed the surface of the titanium dioxide compound can also be used.

These titanium dioxides are preferably added in an amount of 1 to 30 parts by weight based on 100 parts by weight of the vinyl chloride resin.

Examples of the alkyl group having 6 to 30 carbon atoms which may be substituted for the alkyl phosphate metal salt or the basic metal salt represented by the general formulas (I) and (II) include hexyl and isohexyl. , it may be mentioned heptyl, octyl, isooctyl, 2-ethylhexyl, decyl, isodecyl, lauryl, tridecyl, C _{12 to 15} mixed alkyl, myristyl, cetyl, stearyl, eicosyl, behenyl, hexacosyl, octacosyl, triacontyl and the like.

Examples of the divalent or trivalent metal component include alkaline earth metals such as magnesium, calcium, strontium, and barium, zinc, and aluminum. Among these, aluminum is particularly preferred as the metal component, and as the metal salt, Basic metal salts are preferred.

The addition amount of these alkyl phosphate metal salts or basic metal salts is 0.01 to 10, preferably 0.05 to 10 parts by weight.
5 parts by weight.

The composition of the present invention may be used in combination with a metal organic acid salt (such as a normal metal soap, a lead-based stabilizer, and an organotin-based stabilizer). Examples of the metal constituting these metal organic acid salts include Li, Na, K, Mg, Ca, Ba, Zn,
There are Sn, Sr and the like, and the organic acid residues include the following carboxylic acid and phenol residues.

Examples of carboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, neodecanoic acid, 2-ethylhexylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid,
Myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, P-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-dicarboxylic acid Tributyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid, N, N-dimethylbenzoic acid, acetoxybenzoic acid, salicylic acid, P- Trioctyl salicylic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid, monovalent carboxylic acids such as octylmercaptopropionic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, Pimelic acid, spearic acid, azelaic acid, sebatenoic acid, phthalic acid Dicarboxylic acids such as isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, aconitic acid, and thiodipropionic acid; and monoesters of these divalent carboxylic acids or Examples thereof include monoamide compounds, trivalent or tetravalent carboxylic acids such as hemimelitic acid, trimellitic acid, melophanic acid and pyromellitic acid, and di- or triester compounds of these trivalent or tetravalent carboxylic acids.

Examples of phenols include, for example, tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n
-Butyl phenol, isoamyl phenol, ethyl phenol, isopropyl phenol, isooctyl phenol, 2-ethylhexyl phenol, tertiary nonyl phenol, decyl phenol, tertiary octyl phenol, isohexyl phenol, octadecyl phenol, diisobutyl phenol, methyl propyl phenol, dia Milphenol, methyliohexylphenol, methyl-tert-octylphenol and the like can be mentioned.

Examples of the lead stabilizer used in the present invention include:
Lead white, basic lead silicate, basic lead sulfate, dibasic lead sulfate,
Tribasic lead sulfate, basic lead sulfite, dibasic lead phosphite,
Silica gel coprecipitated lead silicate, dibasic lead phthalate, acid-basic lead maleate, lead salicylate, lead stearate, basic lead stearate, dibasic lead stearate, lead laurate, lead octylate, 12- Lead hydroxystearate, lead behenate, lead naphthenate and the like can be mentioned.

Examples of the organic tin compound include, for example, methylstannoic acid, butylstannoic acid, octylstannoic acid, dimethyltin oxide, dibutyltin oxide,
Dioctyltin oxide, dimethyltin sulfide, dibutyltin sulfide, dioctyltin sulfide, dicyclohexyltin sulfide, monobutyltin oxide sulfide, methyl thiostannoic acid, butyl thiostannoic acid, octyl thiostannoic acid, dibutyl tin dilaurate, Dibutyltin distearate, dioctyltindiolate, dibutyltin basic laurate,
Dibutyltin dicrotonate, dibutyltin bis (butoxydiethylene glycol malate), dibutyltin methyl
Octyl maleate / neopentyl maleate, dibutyl tin octyl maleate / 1,4-butanediol malate, dibutyl tin dimethacrylate, dibutyl tin dicinnamate,
Dioctyltin bis (oleyl maleate), dibutyltin bis (stearylmalate), dibutyltin itaconate,
Dioctyl rutin malate, diamyl tin bis (cyclohexyl malate), dimethyl tin dicrotonate, diethyl tin bis (isooctyl citraconate), dipropyl tin bis (benzyl malate), diisobutyl tin bis (propyl malate), dicyclohexyl tin malate, Dioctyltin bis (butylmalate), dibutyltin dimethoxide, dibutyltin dilauroxide, dioctyltin ethyleneglycoxide, pentaerythritol / dibutyltin oxide condensate, dibutyltin bis (laurylmercaptide), dimethyltinbis (stearylmercaptide),
Monobutyltin tris (lauryl mercaptide), dibutyltin-β-mercaptopropionate, dioctyltin-β-mercaptopropionate, dibutyltin mercaptoacetate, monobutyltin tris (isooctylmercaptoacetate), monooctyltin tris ( 2-ethylhexylmercaptoacetate), dibutyltin bis (isooctylmercaptoacetate), dioctyltinbis (isooctylmercaptoacetate), dioctyltinbis (2-ethylhexylmercaptoacetate), dimethyltinbis (isooctylmercaptoacetate), dimethyltin Bis (isooctylmercaptopropionate), monobutyltin tris (isooctylmercaptopropionate), bis [monobutyldi (isooctoxycarbonylmethyle) Thio) sulfide,
Bis [dibutylmono (isooctoxycarbonylmethylenethio) tin] sulfide, monobutylmonochlorotinbis (isooctylmercaptopropionate), monobutylmonochlorotinbis (isooctylmercaptoacetate), monobutylmonochlorotinbis (laurylmercapto) Tide), dibutyltin bis (ethylcellosolve maleate), bis (dioctyltin laurate) malate, bis (dioctyltin butylmalate) malate, bis (methyltin diisooctylthioglycolate) disulfide, bis (methyl / dimethyltin mono) / Diisooctylthioglycolate) disulfide, bis (methyltin diisooctylthioglycolate) trisulfide, bis (butyltin diisooctylthioglycolate) trisulfide, 2-meth Aryloxycarbonyl ethyl tin tris (butyl thioglycolate), 2-methoxycarbonylethyl tin tris (isooctyl thiopropionate), 2-
Butoxycarbonylethyltin tris (stearylthiopropionate), 2-methoxycarbonylethyltin tris (isooctylthioglycolate), 2-methoxycarbonylpropyltin tris (octylthioglycolate), 2-methoxycarbonylethyltin tris ( 2-ethylhexylthiopropionate), 2-methoxycarbonylethyltin sulfide polymer, 2-ethoxycarbonylpropyltin sulfide polymer, 2-butoxycarbonylethyltin sulfide polymer, 2-isopropoxycarbonylethyltin sulfide polymer,
Bis (2-methoxycarbonylethyl) tin bis (isooctylthioglycolate), bis (2-methoxycarbonylethyl) tin bis (2-ethylhexylthioglycolate), bis (methoxycarbonylethyl) tin bis (2
-Ethylhexylthiopropionate), bis (2-butoxycarbonylethyl) tin bis (butylthioglycolate), bis (2-methoxycarbonylethyl) tin bis (stearylthioglycolate), bis (2-ethoxycarbonylpropyl) Tin bis (laurylthioglycolate), bis (2-isopropoxycarbonylethyl) tin bis (isooctylthiopropionate), bis (2-
Methoxycarbonylethyl) tin sulfide polymer,
Bis (2-methoxycarbonylpropyl) tin sulfide polymer, bis (2-propoxycarbonylethyl)
Tin sulfide polymer, bis (2-methoxycarbonylethyl) tin sulfide polymer, bis (2-methoxycarbonylethyl) tin malate polymer, bis (2-
Ethoxycarbonylethyl) tin dilaurate, bis (2
-Methoxycarbonylisopropoxy) tin dilaurate, bis (2-methoxycarbonylethyl) tin bis (isooctylmalate) and the like.

Further, as the vinyl chloride resin used in the present invention, vinyl chloride homopolymer and vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride- Propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-urethane copolymer, vinyl chloride-acrylate copolymer, vinyl chloride -Styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride -Vinylidene chloride-vinyl acetate copolymer, vinyl chloride-maleic acid ester copolymer Vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride copolymer such as vinyl chloride-maleimide copolymer, and the above resin and polyethylene, polypropylene, polybutene, poly-3-methylbutene, etc. α-
Polyolefins such as olefin polymers or ethylene-vinyl acetate copolymers, ethylene-propylene copolymers and copolymers thereof, polystyrene, acrylic resin, polyurethane, styrene and other monomers (for example, maleic anhydride, butadiene, Copolymers with acrylonitrile), acrylonitrile-styrene-butadiene copolymer, acrylate-styrene-butadiene copolymer, and methacrylate-styrene-butadiene copolymer blends.

These vinyl chloride resins may be those obtained by any of conventionally known polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization and bulk polymerization.

In addition, the composition of the present invention includes inorganic metal salts such as hydrotalcite; higher fatty acids such as stearic acid, higher alcohols such as stearyl alcohol, montan wax, paraffin wax, waxes such as polyethylene wax, stearic acid amide, Lubricants such as amides such as methylenebisstearic acid amide and ethylenebisstearic acid amide can also be added, and if necessary, pigments, dyes, fillers, antistatic agents, flame retardants, etc. Can also.

〔Example〕

 Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1 (combination) PVC (Geon 103EP-8) 100 parts by weight Tribasic lead sulfate 2.0 Dibasic lead stearate 0.7 Stearic acid 0.5 Barium stearate 0.5 Lead stearate 1.0 Distearyl phthalate 1.0 Calcium carbonate 10.0 Carbon black 0.2 Titanium dioxide 10.0 Alkyl phosphate metal salt (Table-1) 0.3 After sufficiently mixing the above-mentioned components, the mixture was kneaded with a plastic coder manufactured by Pravender under the following conditions. The plate-out phenomenon was measured from the left and right rotors and the resin stain after the kneaded material was taken out, and the stain was indicated in five stages.

The results are shown in Table 1 below.

(Plastic coder conditions) Jacket temperature 180 ° C Rotation speed 40rpm Input 72g (60cc) Preheating time 6 minutes Kneading time 15 minutes Example 2 (combination) PVC (Geon 103EP-8) 100 parts by weight Dibasic lead stearate 1.0 Lead stearate 1.0 Distearyl phthalate 2.0 Calcium carbonate 10.0 Titanium dioxide 10.0 Acrylic processing aid 1.0 Alkyl metal phosphate (Table-2) 0.5 The above-mentioned composition was measured for the plate-out phenomenon using a plastic coder in the same manner as in Example 1.

 The results are shown in Table 2 below.

Example-3 (Compound) PVC (S-1007) 100 parts by weight Acrylic resin modifier 10.0 Dioctyltin bis (2-ethylhexyl thioglycolate) 1.4 Polyethylene oxide 0.5 Ester lubricant 0.9 Titanium dioxide 10.0 Carbon black 0.2 Barium stearate 0.5 alkyl metal phosphate (Table 3) The above composition was subjected to the same operation as in Example 1 to measure a plate-out phenomenon using a plastic coder.

 The results are shown in Table 3 below.

[Effects of the Invention] From the results of each of the above examples, by adding an alkyl phosphate metal salt or a basic metal salt to a vinyl chloride resin blended with the titanium dioxide compound of the present invention, a plate of a hard vinyl chloride resin was obtained. It is clear that there is an effect of suppressing the out phenomenon.

────────────────────────────────────────────────── (5) References JP-A-59-91144 (JP, A) JP-A-63-168462 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 27/06 C08K 3/22 C08K 5/521

Claims (1)

(57) [Claims] (1) 1 to 30 parts by weight of titanium dioxide based on 100 parts by weight of a hard vinyl chloride resin and the following general formula (I)
And a hard vinyl chloride resin composition comprising 0.01 to 10 parts by weight of a divalent or trivalent metal salt or a basic metal salt of an alkyl phosphoric acid selected from (II) and (II). (In the formula, R represents an optionally substituted alkyl group having 6 to 30 carbon atoms.)