JPH0696657B2 - Polyvinyl chloride resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a stabilized polyvinyl chloride resin composition. More specifically, it has excellent coloring resistance, weather resistance, and sticking phenomenon on the roll surface (plate-out phenomenon).
And a low odor polyvinyl chloride resin composition with improved additive blowing phenomenon (blooming phenomenon).

[Conventional technology]

It is well known that a polyvinyl chloride resin is colored as a result of overheating during molding or after being a processed product due to photodegradation, mainly of ultraviolet rays, and cannot be an excellent product.
Various stabilizers have been proposed and put to practical use in order to improve such drawbacks.

As is well known, the performance required for a stabilizer of polyvinyl chloride resin is multifaceted in addition to the above heat and light. The stabilizers used conventionally have various characteristics as their effects, and it is not possible to obtain a fully satisfactory stabilizer. Even those which have been put to practical use as relatively excellent stabilizers, stabilizers having further excellent effects are required in order to obtain even more excellent products.

For example, organotin stabilizers have a very good effect. In particular, the organotin mercapto-based stabilizer is a very effective stabilizer which is excellent in heat resistance and initial coloring effect, but has a strong peculiar odor and remains a work environment problem.

Further, organic acid salts of alkaline earth metals are generally excellent in heat resistance but inferior in initial colorability. For this reason, for example, when obtaining a color product, it takes time for delicate color matching and changes due to multi-generation processing temperature and time, and there is a problem that a desired uniform color product cannot be obtained. ing.

Therefore, in order to supplement this, when an organic acid salt of zinc is added to obtain a desired initial coloration, thermal stability and transparency are deteriorated and thermal processing becomes unstable. Further, as a conventional technique, a composition in which a specific metal salt of halogen oxygen acid and another stabilizer are used in combination has been proposed (Japanese Patent Publication No. 57-57056).
Issue, Japanese Examined Sho 57-47925, Examined Sho 57-47926, Examined Sho 57
However, according to the experiments conducted by the present inventor, these cannot be said to be comprehensive as measures for stabilizing polyvinyl chloride resins.

[Disclosure of Invention]

As a result of various investigations in view of these circumstances, the present inventor has excellent coloring resistance by adding at least one of tin salt of perchloric acid and alkyl tin salt to polyvinyl chloride resin,
Moreover, it has been found that a composition having significantly improved plate-out and blooming phenomena can be obtained.

That is, the present invention is characterized by adding 0.01 to 5 parts by weight of at least one tin salt of perchloric acid or an alkyl tin salt as a stabilizer to 100 parts by weight of a polyvinyl chloride resin. A vinyl chloride resin composition is provided.

In the present invention, a tin perchlorate salt or an alkyl tin perchlorate salt may be added alone to the polyvinyl chloride resin together with other stabilizers and additives described below, but two or more of these or these may be added. And perchloric acid can be used together.

Next, the tin salt and alkyl tin salt used in the present invention are
For example, it is manufactured as follows. That is, tin or its oxide, hydroxide, or alkyltin oxide is added while stirring the aqueous solution of perchloric acid. It is synthesized by sufficiently stirring, reacting, and then filtering, and filtering the crystallized product from the filtrate, or removing water from the filtrate and drying.

At this time, it is also possible to add perchloric acid in excess and to add perchloric acid, tin salt and alkyl tin salt in the product to the resin.

The tin salt of perchloric acid and the alkyl tin salt used in the present invention are
Each or two or more or a total of these and perchloric acid is 0.01 to 5 per 100 parts by weight of the polyvinyl chloride resin.
Parts by weight, preferably 0.05 to 3 parts by weight.

[Resin for stabilization]

The polyvinyl chloride-based resin to be stabilized in the present invention is composed mainly of polyvinyl chloride and vinyl chloride,
It is a copolymer with a monomer copolymerizable therewith, a graft polymer, a block polymer and a polymer blend containing these as the main components.

[Other Additive Stabilizers] In the present invention, in addition to the above-mentioned tin salt of perchloric acid and the stabilizer of alkyl tin salt, stabilizers of conventionally known polyvinyl chloride resins, for example, the following are shown. Stabilizers can be included.

That is, it is an acidic, neutral, or basic organic acid salt of group Ia, group IIa, group IIb, or group IVb, and organic acids used for these are 2-
Ethylhexoic acid, neoic acid, lauric acid, stearic acid, isostearic acid, hydroxystearic acid, ricinoleic acid, oleic acid, caproic acid, palmitic acid, 12
-Hydroxystearic acid, myristic acid, octylic acid, isooctylic acid, phenylstearic acid, or dibasic acids such as maleic acid, malonic acid, sebacic acid, azelaic acid, adipic acid, phthalic acid, cyclohexanedicarboxylic acid, and the number of carbon atoms 1 to 18 straight chain or side chain, substituted or unsubstituted, saturated or unsaturated with alcohol, alkoxy alcohol or a hydroxy compound of cycloalkyl, arylalkyl, aryl or alkylaryl having 5 to 18 carbon atoms in total Substituted or unsubstituted aliphatic mono- or dicarboxylic acid such as semi-ester, benzoic acid, methylbenzoic acid, t-butylbenzoic acid, cinnamic acid, salicylic acid, naphthenic acid, pyrrolidonecarboxylic acid, acetoacetic acid ester and its condensate , Benzoylacetone, dibenzoylmethane, stearo Ilbenzoylmethane, rosin acid, octylphenol, nonylphenol, t-butylphenol and the like.

Other stabilizers such as organotin compounds may be used in combination. Examples include mono- or dialkyltin fatty acid salts or aromatic acid salts, mono- or dialkyltin maleic acid salts and polymer salts, mono- or dialkyltin maleic acid ester salts, mono- or dialkyltin mono- or dimaleic acid ester salts, mono- or di-fatty acid salts, Mono- or di-alkyl tin mono- or di-maleic acid ester salt Mono- or di-aromatic acid salt, mono- or di-alkyl tin mercapto carboxylic acid salt and polymer salt, mono- or di-alkyl tin sulfide and polymer salt, mono- or di-alkyl tin mercapto carboxylic acid ester salt, mono Or dialkyltin mercaptocarboxylic acid ester mono or disulfide, mono or dialkyltin mercaptocarboxylic acid ester oxide salt, mono or dialkyltin mercaptide, mercapto acid ester salt,
Mono- or dialkyl tin fatty acid alkyl mercaptide mono- or disulfide, tin compounds described in JP-A-51-44149 and the like.

Furthermore, an organic non-metal stabilizer may be used in combination as long as it does not impair the object. Examples of these organic non-metal stabilizers include 2-phenylindole, diphenylthiourea,
Cetyl and stearyl β-aminocrotonate,
1,3 and 1,4-butanediol bis β-aminocrotonic acid ester, thiodiethylene glycol bis β-aminocrotonic acid ester, isocyanuric acid and its derivatives such as nitrogen-containing compounds such as tris (2-hydroxyethyl) cyanurate, penta Polyhydric alcohols such as erythritol, mannitol, sorbitol, benzoic acid, methylbenzoic acid, glycolic acid, maleic acid, cinnamic acid, p-
Tertiary butylbenzoic acid, carboxylic acids such as crotonic acid, acetoacetic acid esters and condensates thereof, boric acid esters, thiodiglycolic acid esters, malonic acid mono- or diesters, benzoylacetone, dibenzoylmethane,
Β- such as stearoylbenzoylmethane and dehydroacetic acid
Examples include diketones.

[Other additives]

An antioxidant may be used in the composition of the present invention if necessary. As these antioxidants, hindered phenols,
A phenolic antioxidant containing a phenol derivative such as poly (alkylphenol) bound via alkylene or alkylidene, poly (alkylphenol) bound via sulfur, alkanoic acid bound to sulfur and its alkyl There are sulfur-containing compounds such as esters, for example, lauryl stearyl thiodipropionate and dilauryl thiodipropionate. Phosphite, tris cyclohexyl phenyl phosphite, tris phenyl phenyl phosphite, tris (dipropylene glycol) phosphite,
Tris (ethoxyethoxyethyl) phosphite, tris [4,4'-butylidenebis (2-t-butyl-5-methylphenol)] phosphite, diphenylphosphite, mono-2-ethylhexylphosphite, tetra (tridecyl) -4 , 4'-isopropylidene diphenyl diphosphite, tetra (phenyl) dipropylene glycol diphosphite, heptakis (nonylphenyl)
Tetrakis (bisphenol A) pentaphosphite,
Heptakis (nonylphenyl) tetrakis (bisphenol A) pentaphosphite, heptakis (dipropylene glycol) triphosphite, bis (neopentyl glycol) dipropyleneglycol diphosphite,
Tetrakis (butoxyethoxyethyl) ethylene glycol diphosphite, bis (cyclohexylphenyl)
Bis (phenylethyl) 1,4-dibutanediol diphosphite, potassium didecyl phosphite, zinc di (octyl phosphite), calcium butoxyethoxyethyl phosphate, stearic acid dilauryl barium phosphite, tricresyl phosphate, trioctyl Phosphate, tris (butoxyethyl) phosphate, xylenyl diphenyl phosphate, monolauryl phosphate, lauryloxy polyethoxy phosphate, di-t-butyl phenoxy polyethoxy phosphate, oleyloxy polyethoxy dilauryl phosphate Ate, other spiro type phosphite such as distearyl pentaerythritol diphosphite, didecyl pentaerythritol diphosphite, diphenylenylerythritol didecyl phosphite, cage phosphite And tris (laurylthio) phosphite, tetrakis (mercapto octyl) 1,6
There are dimethylcaptohexylenediphosphite, pentakis (dodecylmercapto) bis (1,6-hexylenedimercapto) triphosphite, phosphite such as 0,0'-diisopropylthiol phosphate, zinc dibutyldithiophosphate, and phosphate.

If an ultraviolet absorber is added to the present invention, weather (light) resistance can be improved. Therefore, they are used alone or in combination depending on the purpose of use. These include benzophenone-based, benzotriazole-based, salicylate-based, cyanoacrylate-based, hindered amine-based, metal chelate-based salts, particularly nickel and chromium salts. Further, phthalate ester-based plasticizers or other ester-based plasticizers, polyester-based plasticizers, phosphoric acid ester-based plasticizers, chlorine-based plasticizers, other plasticizers, and further epoxy-based compounds such as epoxidized soybean oil and epoxidized Epoxidized vegetable oils such as linseed oil, butyl epoxy stearate, octyl epoxy stearate, 2-ethylhexyltol oil fatty acid ester, epoxy stearyl epoxy stearate, epoxidized tetrahydrophthalic acid dioctyl ester, epoxidized cyclohexane dicarboxylic acid distearyl Epoxy compounds of epoxy resins such as epoxidized esters and polycondensates of 4,4'-isopropylidene diphenol and epichlorohydrin may be used in combination, if necessary.

If necessary, oxides, hydroxides, chlorides, sulfides, carbonates, sulfates of metals of Group I to V or VIII of the periodic table,
Inorganic metal compounds such as sulfites, phosphates, phosphites, silicates, chlorates, perchlorates, borates, etc. may also be used. Examples include calcium carbonate, calcium oxide,
Calcium hydroxide, zinc oxide, zinc oxide, zinc hydroxide,
Zinc carbonate, zinc sulfide, zinc phosphite, zinc borate, barium perchlorate, magnesium oxide, magnesium hydroxide,
Magnesium carbonate, aluminum oxide, aluminum hydroxide, alumina, sodium silicate, aluminum silicate, magnesium silicate, calcium silicate, A type, X
-Type, Y-type, etc. synthetic zeolites, natural zeolites such as analsite, mordenite, etc., or zeolite Ia of these
Silicate metal salts such as metal-substituted zeolites in which the group metal is substituted with a Group II or Group IV metal ion, activated clay, talc, clay, red iron oxide, bentonite, kaolin, diatomaceous earth, hydrotalcite, asbestos , Antimony trioxide, barium hydroxide, barium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium sulfate and the like. In addition, a fluorescent agent, an antibacterial germicide, a plate-out prevention agent, an antifogging agent, a cross-linking agent, a lubricant, a surfactant, a reinforcing agent, a processing aid, a release agent, a viscosity reducing agent, etc. are used as the polyvinyl chloride of the present invention. It can be included in the resin composition.

[Examples and effects] Next, examples show the stabilizing effect of the polyvinyl chloride resin according to the present invention.

In the following examples, the heat resistance test shows the time until reaching a black color in the gear oven test, the initial coloring property shows after 5 minutes, and the heat aging property shows after 400 hours. For Bloom, the press sheet was immersed in tap water for 24 hours and then air-dried to compare blooming states. The weather resistance evaluation shows the deterioration state after 500 hours by a weather meter.

The test results of initial colorability, heat aging resistance, plate-out, bloom and weather resistance are evaluated by showing the stages with the following symbols.

Example 1 The additives shown in Table 1 were dry-blended to the following basic composition,
A sheet was made by kneading with a two-roll machine at ℃ for 10 minutes. The sheet was tested in a gear oven at 175 ° C. A press sheet was prepared from this sheet under the conditions of 175 ° C and 100 kg / cm ² . Heat resistance at this time, initial colorability,
Table 1 shows the plate-out condition of the roll surface during blooming and kneading.

Basic compound Polyvinyl chloride resin 100 parts by weight Dioctyl phthalate 50 〃 Epoxidized soybean oil 0.4 〃 Calcium stearate 0.4 〃 Didecyl monophenyl phosphite 0.5 〃 Example 2 The following basic formulation was dry blended with the additives of Table 2 to give 175
A sheet was made by kneading with a two-roll machine at ℃ for 10 minutes. About this sheet Heat resistance in gear oven at 175 ℃,
The initial colorability, heat aging resistance at 110 ° C. and weather resistance were tested. The results are shown in Table 2.

Basic composition Polyvinyl chloride resin 100 parts by weight MBS 10 〃 ABS 3 〃 Epoxidized soybean oil 3 〃 Barium stearate 0.6 〃 Zinc stearate 0.4 〃 In addition to the above examples, combinations of tin perchlorate salt and alkyl tin salt have the same effect.

The above examples show that the compositions of the present invention exhibit superior effects in all the stabilizing aspects required for polyvinyl chloride resins compared to known compositions.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 61-34042 (JP, A) JP 60-94440 (JP, A) JP 58-173159 (JP, A) JP 58- 127751 (JP, A) JP-A-53-11948 (JP, A) JP-A-58-122951 (JP, A) JP-A-59-140261 (JP, A)

Claims (1)

[Claims] 1. A polychlorinated product characterized by adding 0.01 to 5 parts by weight of at least one tin salt of perchloric acid or an alkyl tin salt as a stabilizer to 100 parts by weight of a polyvinyl chloride resin. Vinyl resin composition.