JP2609879B2 - Stabilizer composition for polyvinyl chloride resin - Google Patents

Description

TECHNICAL FIELD The present invention relates to a stabilizer composition for polyvinyl chloride resins.

More particularly, the present invention relates to a stabilizer composition which gives a polyvinyl chloride resin composition an effect of improving thermal stability, color resistance, transparency and a plate-out phenomenon.

[Conventional technology]

In general, it is well known that a polyvinyl chloride resin cannot be made into an excellent product due to light deterioration mainly due to ultraviolet rays after heating during molding or a processed product.
Conventionally, various stabilizers have been proposed and put to practical use in order to improve such disadvantages. For example, metal soaps, organotin compounds, epoxy compounds, organic phosphites, antioxidants, ultraviolet absorbers and the like have been added alone or in any combination thereof, but the effects are still satisfactory. In addition, there has been a demand for a stabilizer having even better effects.

[Problems to be Solved by the Invention and Means Therefor]

The present inventors have conducted intensive studies in view of these points, and as a result, it has been found that a combination composition of certain phosphoric acids and phosphite compounds has thermal stability,
The present invention has been found to bring about a remarkable effect in improving the coloring resistance, transparency and plate-out phenomenon, and has reached the present invention.

The present invention provides the following: (a) General formula (1) [In the formula, R ₁ , R ₂ and R ₃ are the same or different alkyl, aryl, arylalkyl and monoalkylaryl groups, and at least one of R ₁ and R ₂ is a dialkylaryl group. And (b) a stabilizer composition for a polyvinyl chloride resin containing one or more of phosphorous acid or a phosphoric acid compound having at least one hydroxyl group directly linked to phosphorus.

The following are examples of the compounds (a) and (b) used in the present invention.

[Specific description of invention constituent requirements]

(A) Compound represented by general formula (1) No. 1 di-octyl mono-dimethyl phenyl phosphate No. 2 di-phenyl mono-dimethyl phenyl phosphate No. 3 di-methyl phenyl mono-dimethyl phenyl Phosphate No. 4 Di-t-butyl phenyl mono-dimethyl phenyl phosphate No. 5 Di-lauryl mono-di-t-butyl phenyl phosphate No. 6 Di-benzyl mono-di-t-butyl phenyl Enyl phosphate No. 7 Di-octyl phenyl mono-di-t-butyl phenyl phosphate No. 8 Di-tridecyl mono-dinonyl phenyl phosphate No. 9 Di-methyl phenyl mono-dinonyl phenyl phosphate Ethate No.10 di-nonylphenyl mono-dinonylphenyl phosphate No.11 mono-tridecyldi-dimethylphenyl phosphate No.12 mono-phenyl Di-dimethyl phenyl phosphate No. 13 Mono-methyl phenyl di-dimethyl phenyl phosphate No. 14 Mono-nonyl phenyl di-dimethyl phenyl phosphate No. 15 Mono-lauryl di-di-t-butyl phenyl phosphate No. 16 Mono-benzyldi-di-t-butylphenylphosphate No.17 Mono-octyldienyldi-di-t-butylphenylphosphate No.18 Mono-octyldi-dinonylphenylphosphate No.19 Mono- Phenyl di-dinonyl phenyl phosphate No. 20 mono-t-butyl phenyl di-di nonyl phenyl phosphate (b) Phosphorous acid or phosphoric acid compound having at least one hydroxyl group directly linked to phosphorus is represented by the general formula (Wherein R _{1 to} R ₅ are the same or different hydrogen, alkyl, cycloalkyl, aryl, alkylaryl, alkenyl, arylalkenyl, and these groups including epoxy or H _2m C _m O _X Z ₁ , or- Z ₂ OC _m H _{2m + 1} is shown.

Z ₁ is hydrogen, alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl group Z ₂ is aryl, or these substituted groups m is 1 to 9, x is 1 to 10 Y is a polyhydric alcohol residue, or These substituted groups n are 0-10, A is 0 or 1, W is absent or oxygen and has at least one hydroxyl group directly linked to phosphorus, ie, R ₁ -R ₅
At least one is hydrogen.

(The hydroxyl group in the present invention represents> P-OH, but since these compounds take tautomerism, Is also meant. )].

As a specific example, No. 21 (C ₃ H ₇ O) ₂ POH No. 22 C ₃ H ₇ OP (OH) ₂ No. 23 (C ₁₀ H ₂₁ O) ₂ POH [Resin to be Stabilized] The polyvinyl chloride resin to be stabilized in the present invention is polyvinyl chloride and a copolymer or graft polymer of a monomer having vinyl chloride as a main component and copolymerizable therewith. , Block polymers and polymer blends containing these as main components.

Stabilizer of the present invention, these polyvinyl chloride resin 100
0.005 to 8.0 parts by weight of the compound represented by the general formula (1) and (b) a phosphorous acid or phosphoric acid compound having at least one hydroxyl group directly linked to phosphorus is used in the general formula (1). The compound is usually used in a weight ratio of 1: 0.01-1.

[Other additives]

In the present invention, the following stabilizers can be contained as needed.

That is, acidic, neutral, basic Ia group, IIa group, IIb group, I
V b group organic acid salts and the organic acids used therein include 2-ethylhexoic acid, neo acids, lauric acids, stearic acid, isostearic acid, hydroxystearic acid, myristic acid, octylic acid, isooctylic acid, phenyl Stearic acid, or dibasic acid such as maleic acid, malonic acid, sebacic acid, azelaic acid, adipic acid, phthalic acid, cyclohexanedicarboxylic acid, and a linear or side chain having 1 to 18 carbon atoms, substituted or unsubstituted, Substituted or unsubstituted aliphatic mono- or dicarboxylic acids such as saturated or unsaturated alcohols, alkoxy alcohols or cycloesters having a total of 5 to 18 carbon atoms, such as cycloalkyls, arylalkyls, aryls and alkylaryl hydroxy compounds; In addition, benzoic acid, methylbenzoic acid, t-butylbenzoic acid, cinnamic acid, salicylic acid Examples thereof include acid, naphthenic acid, pyrrolidonecarboxylic acid, acetoacetic acid ester and its condensate, benzoylacetone, dibenzoylmethane, stearoylbenzoylmethane, rosin acid, octylphenol, nonylphenol, and t-butylphenol.

Other stabilizers such as organotin compounds may be used in combination. Examples are mono- or di-alkyltin fatty acid salts or aromatic acid salts, mono- or dialkyltin arinates,
Mono or dialkyl tin maleate, mono or dialkyl tin sulfide, mono or dialkyl tin mercapto carboxylate, mono or dialkyl tin mercapto carboxylate, mono or dialkyl tin mercapto carboxylate sulfide, mono or dialkyl tin Mercaptocarboxylic acid ester oxide salts, mono- or dialkyltin mercaptoalkylcarboxylates,
Examples include mono- or di-alkyl tin mercapto alkyl carboxylic acid sulphide salts and tin compounds described in JP-A-51-44149.

Further, organic non-metal stabilizers may be used in combination as long as the object of the present invention is not hindered.

Examples of these organic nonmetal stabilizers include 2-phenylindole, diphenylthiourea, cetyl and stearyl β-aminocrotonate, 1,3 and 1,4-butanediol bisβ-aminocrotonate, and thiodiethylene glycol bisβ. -Aminocrotonate,
Isocyanuric acid and its derivatives, for example, nitrogen-containing compounds such as tris (2-hydroxyethyl) cyanurate, polyhydric alcohols such as pentaerythritol, mannitol, sorbitol, benzoic acid, methylbenzoic acid, glycolic acid, maleic acid, cinnamic acid, p Carboxylic acids such as tertiary butyl benzoic acid, crotonic acid, acetoacetate and condensates thereof, borate, thiodiglycolate, malonic acid mono- or diester and benzoylacetone, dibenzoylmethane, stearoylbenzoylmethane, dehydroacetic acid And β-diketones.

An antioxidant may be used in the composition of the present invention if necessary.

These antioxidants include phenolic antioxidants containing phenol derivatives such as hindered phenols, poly (alkylphenols) bound via alkylene or alkylidene, poly (alkylphenols) bound via sulfur, and sulfur There are ionic compounds such as alkanoic acid and its alkyl ester bonded together, for example, lauryl stearyl thiodipropionate and dilauryl thiodipropionate, and further, triphenyl phosphite, tridecyl phosphite, monophenyl didecyl phosphite. Phyto, tricresyl phosphite, tris nonyl phenyl 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 4,4'-isopropylidenediphenyldiphosphite, tetra (phenyl) dipropylideneglycol diphosphite, heptakis (nonylphenyl) tetrakis (bisphenol A) pentaphosphite, heptakis (nonylphenyl) tetrakis (bisphenol A) pentaphos Phite, heptakis (dipropylene glycol) triphosphate, bis (neopentyl glycol) dipropylene glycol diphosphite, tetrakis (butoxyethoxyethyl) ethylene glycol diphosphite Bis (cyclohexylphenyl) bis (phenylethyl) 1,4-dibutanediol diphosphite, potassium didecyl phosphite, zinc di (octyl phosphite), calcium butoxyethoxyethyl phosphate, barium stearyl dilauryl phosphite, tricresyl Phosphate, trioctyl phosphate, tris (butoxyethyl) phosphate, distearylpentaerythritol diphosphate, didecylpentaerythritol diphosphite, diphenylpentaneerythritol diphosphite, tris (laurylthio) phosphite, tetrakis (mercaptooctyl) 1,6-Dimercaptohexylenediphosphite, pentakis (dodecylmercapto) bis (1,6-hexylenedimercapto) triphosphite, 0,0'-diisopropylthio Phosphates, such as Jibuchirujichio phosphoric acid zinc phosphite, there is phosphates.

Weather resistance (light) if an ultraviolet absorber is added to the composition of the present invention
It can be used alone or in combination depending on the purpose of use, because it can improve the properties. These include benzophenone based, benzotriazole based, salicylate based, cyanoacrylate based, hindered amine based, metal chelate based especially nickel and chromium salts. Also, phthalate ester plasticizers or other ester plasticizers or polyester plasticizers, phosphate ester plasticizers, chlorine plasticizers, other plasticizers, and epoxy compounds such as epoxidized soybean oil, epoxidized Epoxidized vegetable oils such as linseed oil, butyl epoxy cystearate, octyl epoxy stearate, 2-ethylhexyl tol oil fatty acid ester, epoxy stearyl epoxy stearate,
Epoxy compounds of epoxy resins such as epoxidized esters such as epoxidized tetrahydrophthalic acid dioctyl ester, epoxidized cyclohexanedicarboxylate distearyl, and polycondensates of 4,4'-isopropylidene diphenol and epichlorohydrin may also be used, if necessary. Can be used in combination.

In addition, if necessary, oxides, hydroxides, chlorides, sulfides, carbonates, sulfates, sulfites, phosphates, phosphites, silicic acids of metals of Group I to V or VIII of the periodic table Inorganic metal compounds such as salts, chlorates, perchlorates, borates and the like can also be used. Examples thereof include calcium carbonate, calcium oxide, calcium hydroxide, zinc oxide, zinc chloride, 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 metal-substituted zeolites in which the Group Ia metal of these zeolites is substituted with Group II or Group IV metal ions And metal silicates such as activated clay, talc, clay, red iron oxide, bentonite, carion, diatomaceous earth, hydrotalcite, asbestos, antimony trioxide, barium hydroxide, barium carbonate, potassium hydroxide, barium sulfate, etc. . Other fluorescent agents, anti-bacterial germicides, plate-out prevention agents, anti-fog agents, cross-linking agents,
A lubricant, a surfactant, a reinforcing agent, a processing aid, a release agent, a viscosity reducing agent and the like can be used together with the stabilizer composition for a polyvinyl chloride resin of the present invention.

[Examples and effects]

Next, the stabilizing effect of the polyvinyl chloride resin according to the present invention will be described by way of examples.

The results of the test results used in the examples are indicated by the following symbols.

Example 1 In order to examine the stabilizing effect of the phosphorus compound used in the present invention on a polyvinyl chloride resin, a composition having the following composition was kneaded with two rolls at 170 ° C. for 10 minutes to form a sheet.

Using this sheet, a thermal stability test was conducted in a gear oven at 170 ° C. to compare the degree of discoloration. Also this sheet
It was pressed at 170 ° C. and 100 kg / cm ² for 5 minutes to compare the transparency and the colorability.

 The results are shown in Table-1.

Blended polyvinyl chloride resin 100 parts by weight Dioctyl phthalate 40 〃 Epoxidized soybean oil 2.0 〃 Zinc stearate 0.6 〃 Calcium stearate 0.4 〃 Didecyl monophenyl phosphite 0.5 〃 Phosphorus compound (Table-1) Example 2 In order to examine the stabilizing effect of the phosphorus compound used in the present invention on the polyvinyl chloride resin, the composition of the following formulation A was kneaded with two rolls at 170 ° C. for 10 minutes. The mixture was kneaded for 5 minutes under the same conditions using Formulation B in order to check the extent of the pigment plated out on the roll surface. At that time, the effect of the stabilizer of the present invention on the plate-out was evaluated by the degree of coloring by the pigment applied to the sheet.

 Table 2 shows these results.

Formulation A Polyvinyl chloride resin 100 parts by weight Dioctyl phthalate 40 〃 Barium / cadmium / zinc liquid stabilizer 1.2 〃 Cadmium / lead / barium composite soap 0.6 〃 Watering grade pigment 3.0 燐 Phosphor compound (Table-2) Formulation B Poly 100 parts by weight of vinyl chloride resin Dioctyl phthalate 40 カ Cadmium stearate 2.0 〃 As described above, as a result of the stabilization test, based on the present invention, (a) a phosphorus compound represented by the general formula [I] and (b) a phosphorous acid or a phosphoric acid compound having at least one hydroxyl gas directly linked to phosphorus It was clarified that the stabilizer composition contained together exerts a remarkable synergistic effect on the polyvinyl chloride resin in terms of heat stability, coloring resistance, and improvement of the plate-out phenomenon.

Claims (1)

(57) [Claims] (1) General formula (1) [In the formula, R ₁ , R ₂ and R ₃ are the same or different alkyl, aryl, arylalkyl and monoalkylaryl groups, and at least one of R ₁ and R ₂ is a dialkylaryl group. And (b) a stabilizer composition for a polyvinyl chloride resin containing a phosphorous acid or a phosphoric acid compound having at least one hydroxyl group directly linked to phosphorus.