JPS6126809B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel chlorine-containing resin composition. Generally, in resins containing chlorine, hydrogen chloride is eliminated by heat during molding, resulting in undesirable coloring. Therefore, one or more stabilizers have been added to resin compositions to reduce this coloration at processing temperatures. Conventional stabilizers include tribasic lead sulfate,
Lead-based stabilizers such as tribasic lead maleate and lead stearate and stabilizers such as cadmium stearate have excellent performance, but their toxicity is a problem.
In recent years, various non-toxic or low-toxic stabilizers have been proposed to replace these and have come into widespread use. Specific examples of such stabilizers include lithium,
Calcium, sodium, potassium, barium,
There are salts of metals such as magnesium, strontium, zinc, aluminum, and tin with organic carboxylic acids having 2 to 20 carbon atoms, or phenolates of these metals. For example, lithium stearate, calcium myristate, barium stearate, strontium stearate,
Zinc stearate, magnesium laurate, barium nonylphenol, zinc butylbenzoate,
Examples include zinc ricinoleate, barium oleate, zinc 2-ethylhexylate, calcium naphthenate, zinc isostearate, and various other compounds such as organotin compounds, organophosphorus compounds, and epoxy compounds. Usually, these compounds are used alone or in combination, but each has its own merits and demerits, such as the ability to prevent coloration being often insufficient, and so far they have not been fully satisfactory for practical use. In view of the above-mentioned circumstances, the present invention has developed a stabilizer having excellent stability against deterioration due to heat and low toxicity as a result of careful experimental research. That is, the present invention provides a chlorine-containing resin with the general formula [] (However, R ₁ and R ₃ are aryl groups with 1 to 18 carbon atoms, alkyl groups, aralkyl groups, halogen-substituted alkyl groups, hydroxy-substituted alkyl groups, carboxylic acid-substituted alkyl groups, acyl-substituted alkyl groups, hydroxyl groups, alkoxy or an alkoxy-substituted allyl group. _{R 2} is a hydrogen alkyl group or an aralkyl group, and R ₁ and R ₃ may be the same or different. Also, R ₁ , R ₂ , and R ₃ are mutually terminal. may be bonded.Also, R ₂ may form a dimer.) Compounds represented by and general formula [] (However, R ₁ , R ₂ , R ₄ , R ₆ , and R ₇ have 1 to 18 carbon atoms.
an alkyl group, an aryl group, a phenyl group, an alkyl-substituted phenyl group, or a group represented by R ₃ O—R ₉ O—R ₁₀ —, where R ₈ is hydrogen or has 1 to 4 carbon atoms.
The alkyl group, R ₉ and R ₁₀ are alkylene groups having 2 to 4 carbon atoms. R ₃ and R ₅ are alkylene,
alkylidene, alicyclidene, arylene, aralkylene, alkalylene, cycloalkylene,
A divalent spirocyclic group or a group represented by (-R ₁₁ O-) _l R ₁₂ --, R ₁₁ and R ₁₂ are alkylene groups having 1 to 4 carbon atoms, and 1 is an integer of 0 to 2. . n is 0
means an integer between ~10. ) The present invention provides a chlorine-containing resin composition characterized by adding an organic phosphite compound represented by: Compounds of the formula [] include benzoylpyruvic acid, diacetylacetone, β-ketoglic acid, C-
Methylbenzoylacetone, benzoylacetone, dibenzoylmethane, benzotrifluoroacetone, cyclohexane 1,3 dione, dibenzoylethane, dibenzoylpropane, octylbenzoylacetone, 1-phenyl-2,4-pentadione, 1,3-bis( P-methoxyphenyl)
-1,3-propanedione, diethyl acetonedicarboxylate, bisacetylacetone, diphenadione, 5,5'-dimethylcyclohexane 1,3dione, 2,2'-methylenebiscyclohexane 1,
3 dione, 2-benzylcyclohexane 1,3 dione, and the like. In addition, it is known that normally in these β-diketone compounds, the hydrogen at the α-position is rearranged toward the carbonyl group to form a ketoenol compound, which has tautomerism with the original β-diketone compound. These general formulas []
The amount of the compound represented by is 0.001 to 1.0 parts per 100 parts of resin. Examples of compounds of general formula [] that can be used in the present invention include tetrakis(phenyl)dipropylene glycol diphosphite, pentakis(phenyl)di(dipropylene glycol)triphosphite,
Hexakis(octylphenyl)tris(dipropylene glycol)tetraphosphite, Hexakis(nonylphenyl)tris(dipropylene glycol)tetraphosphite, Tetrakis(nonylphenyl)dipropylene glycol diphosphite, Heptakis(phenyl)tetrakis(dibropylene glycol) ) Pentaphosphite, heptakis (nonylphenyl) tetrakis (dipropylene glycol) pentaphosphite, octakis (amyl phenyl) pentakis (dipropylene glycol) pentaphosphite, decakis (phenyl) heptakis (dipropylene glycol) octaphosphite, decakis (nonylphenyl) ) heptakis (dipropylene glycol) octaphosphite, decakis (lauryl) heptakis (dipropylene glycol) octaphosphite, decakis (oleyl) heptakis dipropylene glycol) octaphosphite, pentakis (dipropylene glycol) diphosphite,
heptakis (dipropylene glycol) triphosphite, heptakis (dipropylene glycol) tetraphosphite, decakis (phenyl)
heptakis (trimethylene glycol) octaphosphite, decakis (phenyl) heptakis (triethylene glycol) octaphosphite, decakis (phenyl) heptakis (tridipropylene glycol) octaphosphite, decakis (phenyl) heptakis (tri-1,2- butylene glycol) octaphosphite, tetra(ptoxyethyl)dipropylene glycol diphosphite, tetra(butoxydiethylenoxy)dipropylene glycol diphosphite, tetra(phenyl)butylene glycol diphosphite, heptakis(phenyl)tetrakis( triethylene glycol) pentaphosphite, tetradecakis (phenyl) undecakis (dipropylene glycol) dodecaphosphite, tetratridecyl-4,4'-isopropylidene dicyclohexyl diphosphite, tetranonyl phenyl-
4,4'-isopropylidenecyclohexyl diphosphite, tetratridecyl-4,4'-isopropylidene diphenyl diphosphite, diphenyl-pentaerythritol diphosphite, diisostearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite Examples include phosphites and the like. The amount of these organic phosphite compounds added is preferably 0.05 to 3 parts by weight, preferably 0.1 to 1.5 parts by weight, per 100 parts of the resin. The resin composition of the present invention contains a phthalate plasticizer or other ester plasticizer, a polyester plasticizer, a phosphate plasticizer, an epoxy plasticizer, a chlorine plasticizer, and other plasticizers. It can be used as appropriate depending on the purpose. Adding an antioxidant to the resin composition of the present invention can increase the oxidative deterioration prevention properties of the resin composition, so it can be used as appropriate depending on the purpose of use. These antioxidants include phenolic antioxidants, sulfur compounds, and the like. If an ultraviolet absorber is added to the resin composition of the present invention, the photostability can be improved, so it is possible to appropriately select and use these depending on the purpose of use. These include benzophenones, benzotriazoles, salicylates, substituted acrylonitriles, various metal salts or metal chelates, especially nickel or chromium salts or chelates, triazine types, and the like. Others as necessary, such as epoxy stabilizers,
Organic chelators, pigments, fillers, foaming agents, antistatic agents, antifogging agents, plate-out prevention agents, surface treatment agents, lubricants, flame retardants, fluorescent agents, microbicides, bactericidal agents, metal deactivators, Photodegradants, non-metallic stabilizers, epoxy resins, borate esters, thiourea derivatives, processing aids, mold release agents, reinforcing agents, and the like can be included. Examples of chlorine-containing resins used in the present invention include the following. For example, polyvinyl chloride resin,
Vinyl chloride and other monomers, such as vinyl acetate,
Copolymers with ethylene, maleic acid, acrylonitrile, butadiene, styrene, vinylidene chloride, etc., polyvinylidene chloride, chlorinated polyethylene,
Examples include chlorinated polypropylene and chlorinated rubber. The following examples show the effects of the chlorine-containing resin product according to the present invention, but the present invention is not limited to these examples. Example 1 For 100 parts by weight of vinyl chloride resin, 50 parts of dioctyl phthalate, 1.0 parts of barium stearate,
Zinc stearate 0.5 parts, dibenzoylmethane 0.1
and organic phosphite compounds shown in Table 1.
Add 0.6 parts and knead for 5 minutes at a roll temperature of 170℃.
A sheet with a thickness of 0.2 mm was created. This sheet was then pressed at 170° C. for 5 minutes to evaluate initial coloration. Further, the heat resistance of the sheet was tested by measuring the time until blackening in a gear oven at 180°C.

[Table] Example 2 For 100 parts by weight of vinyl chloride resin, 50 parts of dioctyl phthalate, 0.8 parts of barium nonylphenol
A sheet was prepared in the same manner as in Example 1 by adding 0.2 parts of zinc stearate, 0.7 parts of decakis (phenyl) heptakis (dipropylene glycol) octaphosphite, and 0.1 part of the dicarbonyl compound shown in Table 2, and the initial coloring was carried out in the same manner as in Example 1. was tested.

[Table] Example 3 For 100 parts by weight of vinyl chloride resin (95% vinyl chloride, 5% vinyl acetate), 50 parts dioctyl phthalate, 2 parts epoxidized soybean oil, 1.0 parts calcium stearate.
part, zinc toluate 0.5 part, dibenzoylmethane
Example 1 by adding 0.2 parts and 0.5 parts of phosphite compound
A sheet was prepared in the same manner as above and tested for heat resistance and initial colorability.

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Claims (1)

[Claims] 1. General formula [] for chlorine-containing resin (However, R ₁ and R ₃ are aryl groups, alkyl groups, aralkyl groups, halogen-substituted alkyl groups, hydroxy-substituted alkyl groups, carboxylic acid-substituted alkyl groups, acyl-substituted alkyl groups, hydroxyl groups, and alkoxyl groups having 1 to 18 carbon atoms. or an alkoxy-substituted allyl group. _{R 2} is hydrogen, an alkyl group, or an aralkyl group, and R ₁ and R ₃ may be the same or different. Also, R ₁ , R ₂ , and R ₃ are mutually terminal. may be bonded.Also, R ₂ may form a dimer.) Compounds represented by and general formula [] (However, R ₁ , R ₂ , R ₄ , R ₆ , and R ₇ have 1 to 18 carbon atoms.
an alkyl group, an aryl group, a phenyl group, an alkyl-substituted phenyl group, or a group represented by R ₃ O—R ₉ —R ₁₀ —, where R ₈ is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ₉ and R ₁₀ is an alkylene group having 2 to 4 carbon atoms. R ₃ and R ₅ are alkylene, alkylidene, alicyclidene, arylene, aralkylene, alkalylene, cycloalkylene, a divalent spirocyclic group or a group represented by (-R ₁₁ O-) _l R ₁₂ -,
R ₁₁ and R ₁₂ are alkylene groups having 1 to 4 carbon atoms;
is an integer from 0 to 2. n means an integer from 0 to 10. ) A chlorine-containing resin composition characterized by adding an organic phosphite compound represented by: