JPS5856535B2 - Stabilizer composition for halogen-containing resins - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a halogen-containing resin stabilizing composition.

More specifically, the present invention relates to a halogen-containing resin stabilized composition that has excellent coloring resistance, heat resistance, and improved roll surface sticking phenomenon (plate-out phenomenon) and additive blow-out phenomenon (blooming phenomenon).

It is well known that halogen-containing resins become colored due to heating during molding or photodeterioration, mainly caused by ultraviolet rays, after they are made into processed products, making it impossible to produce excellent products.

In order to improve these drawbacks, various stabilizers have been proposed and put into practical use.

As is well known, the performance required of stabilizers for halogen-containing resins is wide-ranging in addition to the above-mentioned heat and light performance.

Conventionally used stabilizers have various characteristics in terms of their effects, and no stabilizer that is fully satisfactory has been obtained.

Even though relatively excellent stabilizers have been put into practical use, stabilizers with even better effects are required in order to obtain even better products.

For example, organotin stabilizers have very good effects.

In particular, organic tin mercapto stabilizers are very effective stabilizers with excellent heat resistance and initial coloring effects, but they have strong peculiar odors and still pose problems in the working environment.

Furthermore, organic acid salts of alkaline earth metals generally have excellent heat resistance, but are poor in initial coloring properties.

For this reason, for example, when obtaining a colored product, not only does it take time to delicately match the color, but it also varies depending on the processing temperature and time, making it difficult to obtain a desired uniform colored product.

Therefore, if an attempt is made to obtain the desired initial coloration by adding an organic acid salt of zinc to supplement this, the thermal stability and transparency will decrease, giving rise to concerns about thermal processing.

As a result of various studies, the present inventors have developed a stabilizer composition for a halogen-containing resin, which is characterized by containing one or more diketo acid ester compounds represented by the following general formula for the halogen-containing resin.

General formula (wherein R,, R2, and R3 represent an alkyl group, an allyl group, an aryl group, an alkylaryl group, an aralkyl group, and an alkoxyalkyl group, and these may be the same or different, respectively.

Further, each of these groups may have various substituents.

), it was discovered that the coloring resistance was excellent, and the heat resistance, blooming, and plate-out phenomena were significantly improved, leading to the present invention.

It has been known to use compounds having a wide range of general formulas, including diketones and triketones, as stabilizers for halogen-containing resins.

However, as a result of many years of research, the present inventors have discovered that a specific diketo acid ester compound, which is not disclosed in the prior art described above, has a particularly remarkable effect, leading to the present invention.

This point will be specifically explained in Examples below.

The halogen-containing resin stabilizing composition of the present invention may include one or more commonly used additives as long as they do not impede the purpose of the present invention.
More than one species can be used together.

For example, alkali or alkaline earth metal organic acid salts, organic layers, phosphoric acid esters, epoxy compounds, organic tin compounds, plasticizers, antioxidants, ultraviolet absorbers, pigments, plate-out inhibitors, fillers, surface treatment agents. , flame retardants, optical brighteners,
Examples include anti-fouling disinfectants, processing aids, mold release agents, viscosity reducers, and fragrances.

Examples of compounds used in the present invention include the following.

Synthesis Example The diketo acid ester compound represented by the general formula used in the present invention is synthesized in the following manner.

That is, -71 mol was added to a completely dehydrated solution, heated and reacted for over 24 hours, and then 1 mol of 1R2C (J' was gradually added, and after heating and reaction, NaCl and the solvent were removed to form ( Here, R1, R2, and R3 are the same as shown in the claims).

It is recognized that the stabilizing effect of the compound shown in this general formula on halogen-containing resins is equivalent to that of the compound shown in this general formula, but considering the economic efficiency of raw materials and other factors, the compound shown in Example 2 above is considered to be the most suitable from an industrial perspective. It will be done.

It is luchloride.

Examples of the alkali or alkaline earth metal organic acid salts used in combination in the present invention include organic acid salts of lithium, sodium, potassium, magnesium, calcium, strontium, barium, zinc, and cadmium, including acidic salts, neutral salts, and basic salts. 5 to 30 unsubstituted, substituted, saturated,
Unsaturated aliphatic or aromatic carboxylic acids such as caproic acid, heptanoic acid, 2-ethylhexoic acid, undecanoic acid, lauric acid, neotridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, and hydroxystearin. acid, dihydroxystearic acid, tonadecanoic acid, arachidic acid, heneicosanoic acid,
Behenic acid, tricosanoic acid, lignoceric acid, pentacosanoic acid, montanic acid, nonacosanoic acid, melisic acid, hentriacotanic acid, synthetic mixed odd-numbered acids with 21 to 31 carbon atoms derived from α-olefins, oleic acid, ricinoleic acid , acrylic acid, lylinic acid, linoleic acid, crotonic acid, acetoacetic acid, isostearic acid, isoctylic acid, neoacid, aliphatic carboxylic acids such as octylic acid, malonic acid, adipic acid, azelaic acid, sepatic acid, phthalic acid , dibasic acids such as thiodipropionic acid and dithiopropionic acid, and these dibasic acids and substituted or unsubstituted alkyl alkoxy alcohols having linear or side chains having 1 to 8 carbon atoms;
Semi-esters of cycloalkyl-, arylalkyl-, aryl-, alkylaryl alcohols having 5 to 18 carbon atoms, benzoic acid, methylbenzoic acid, butylbenzoic acid, benzoylbenzoic acid, phenylacetic acid, salicylic acid, fumaric acid, naphthoate Acids, cyclic acids such as naphthalic acid, abietic acid, dihydroabietic acid, phenylstearic acid, pyrrolidonecarboxylic acid, cinnamic acid, p-tert-butylbenzoic acid, rosin acid, naphthenic acid, dehydroacetic acid, or nonylphenol, octylphenol, t
- Organic acids such as butylphenol and acetoacetate.

The present invention also includes oxides, hydroxides, chlorides, sulfides, carbonates, sulfates, sulfites, phosphates, phosphites, and silicic acids consisting of metals of Groups I to ■ and ■ of the periodic table. Salts, nitrates, nitrites, and phosphates may also be used in combination.

Examples include calcium carbonate, calcium oxide, calcium hydroxide, zinc oxide, zinc chloride, zinc hydroxide, zinc carbonate, zinc sulfide, zinc phosphite, zinc halide, magnesium oxide, magnesium hydroxide, magnesium carbonate, Silicate metal salts such as aluminum oxide, aluminum hydroxide, alumina, sodium silicate, aluminum silicate, magnesium silicate, calcium silicate, zeolite,
These include activated clay, talc, clay, red iron, asbestos, antimony dioxide, barium hydroxide, barium carbonate, sodium hydroxide, potassium hydroxide, barium sulfate, etc.

As mentioned above, the stabilizing composition of the present invention may also include other stabilizers, such as organic nonmetallic stabilizers, organometallic stabilizers, or organotin compounds, as long as they do not impede the purpose of the present invention. Can be used in combination with more than one species.

For example, 2-phenylindole, diphenylthiourea,
cetyl and stearyl β-aminocrotonic acid ester,
Nitrogen-containing compounds such as 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 tris(2-hydroxyethyl) cyanurate, penta Polyhydric alcohols such as erythritol, mannitol, sorbitol, benzoic acid,
Methylbenzoic acid, licolic acid, maleic acid, 2 (3'
-methoxy-4'hydroxyphenyl)indole, zinc dehydroacetate, antimony trisisooctylthioglycolate, cinnamic acid, p-tert-butylbenzoic acid, carboxylic acids such as crotonic acid, boric acid esters, thiodiglycolic acid esters, β-diketones such as acetylacetone, non-metallic compounds such as acetoacetate and dehydroacetic acid or its esters or amides, mono- or diorganotin fatty acid salts, mono- or diorganotin malate compounds,
Organotin compounds such as mono- or di-organotin mercaptide compounds.

Next, the organic phosphorous esters used in the present invention include the following.

That is, the general formula % formula % [R□, R2, R3 are the same or different alkyl, aryl, alkenyl, alkylaryl, aralkyl, cycloalkyl group, or the following formula (R'', R
/// is hydrogen or the same or different C1-4 alkyl group, including isomer groups thereof.

R' is sulfur or a C1-4 alkylene group including an alkylene group.

) completely esterified or a residue with a hydroxyl group remaining, A may be oxygen or sulfur alone, or oxygen and sulfur may optionally coexist.

If A is oxygen, any two of R1t R2t R3 may be hydrogen] (2) (R'0)2 P(OR")n OP(TOR"'
) 3 [Here, R' and R" are the same or different alkyl, aryl, alkenyl, alkylaryl, aralkyl, cycloalkyl group, R"' is a divalent group selected from alkylene groups such as ethylene, propylene, butylene, etc. **n is an integer from 1 to 100.

] (R1, R2, R,, R6 and R7 are alkyl, aryl, alkenyl, alkylaryl, aralkyl,
Cycloalkyl group, R3 and R5 are divalent groups derived from polyalkylene glycol, alkylidene bisphenol, hydrogenated alkylidene bisphenol, n is 1 to 15
[R is a divalent aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an alkylene group interrupted by one oxygen atom, and R1 is an alkyl group having 1 to 20 carbon atoms.

n is O or 1] (R1 and R2 may be the same or different and represent hydrogen, alkyl, aryl, alkenyl, alkylaryl, aralkyl, cycloalkyl, alkoxyalkyl group, A represents a polyhydric alcohol residue ] It is an organic phosphite ester represented by

Examples of the organic phosphite represented by formula (1) include triphenyl phosphite, tricresyl phosphite, triisooctyl phosphite, tridecyl phosphite, tri-2-ethylhexyl phosphite,
Trisnonylphenyl phosphite, tri(octylphenyl) phosphite, tricyclohexylphenyl phosphite, triscyclohexyl phosphite, tridecyl thiophosphite, triisodecyl thiophosphite, phenyl di-2-ethylhexyl phosphite , phenyl diisodecyl phosphite, phenyl dicyclohexyl phosphite, phenyl diisooctyl phosphite, phenyl di(tridecyl) phosphite, phenyl dicyclohexyl phosphite, diphenyl inoctyl phosphite, diphenyl 2 −
Ethylhexyl phosphite, diphenyl indecyl phosphite, diphenyl cyclohexyl phenyl phosphite, diphenyl tricresyl phosphite,
Nonylphenyl di(tridecyl) phosphite, phenyl p-tert-butyl dodecyl phosphite, diisopropyl phosphite, monoisopropyl phosphite, diisodecyl phosphite, diisooctyl phosphite, monoisooctyl phosphite, didodecyl phosphite phyto, monododecyl phosphite, dicyclohexyl phosphite, monocyclohexyl phosphite, dicyclohexyl phenyl phosphite, monodicyclohexylphenyl phosphite, di(p-butylphenyl) phosphite, tetra(tridecyl)- 4,4'isopropylidene diphenol-diphosphite, tetra(tridecyl)-4,4'-butylidenebis(2-tert-butyl-5-methylphenyl) diphosphite, tetraisooctyl(4,4'thiobis(2-tert- butyl-5-methylphenol)] diphosphite, etc., and those represented by formula (2) include tetranonyl phenyl-polypropylene glycol-siphosphite, tetra(tridecyl)
Dipropylene glycol diphosphite, tetratridecyl-4゜4'-impropylidenecyclohexyl diphosphite, etc. Those represented by formula (3) include pentakis (nonylphenyl) bispolypropylene glycol triphosphite, heptakis ( nonylphenyl) tetrakis polypropylene glycol pentaphosphite, heptakis (nonylphenyl) tetrakis (bisphenol A) pentaphosphite, decakis (nonylphenyl) hebutakis (dipropylene glycol) octaphosphite,
Examples of compounds represented by formula (4) such as decaffenylheptadipropylene glycol octaphosphite include tetrakis(inoctoxycarbomethylenethio)1,2oxycarbonylmethylenethioethylene diphosphite, dibutoxycarboethylenethio(pentaerythritol) (tetrathioglycol) diphosphite, diisooctoxycarbomethylenethio(pentaerythritol tetrathioglycol) diphosphite, etc. Those represented by formula (5) include tetrakis(mercaptrauryl) 1,2-dimercapto-ethylene diphosphite, tetrakis (mercaptrauryl) l, 6
-dimercapto-hexylene diphosphite, tetrakis (mercaptrauryl) β, β'-dimercapto-ethyl ether diphosphite, pentakis (dodecyl-
mercapto)bis(1,6-hexylene dimercapto)
Triphosphite represented by formula (6) includes dibutylpentaerythritol diphosphite, didecylpentaerythritol diphosphite, dioctylpentaerythritol diphosphite, etc., and these are used alone or in combination of two or more. .

Examples of epoxy compounds used in the present invention include epoxidized soybean oil, epoxidized linseed oil, epoxidized lard oil, epoxidized beef tallow oil, epoxidized cottonseed oil, nipoxidized flower oil, epoxidized whale oil, epoxidized tall oil, Epoxidized sunflower oil, epoxidized fish oil, diacetomonoglyceride of epoxidized soybean oil, epoxidized diacetomonoolein, benzoyl epoxystearate, butyl epoxystearate, cyclohexyl epoxystearate, dihydrononyl epoxystearate, 2-epoxystearate Ethyl butyl, methoxyethyl epoxystearate, isodecyl epoxystearate, inoctyl epoxystearate, tetrahydrofuryl epoxystearate, phenyl epoxystearate, acetoxyethyl epoxystearate, butyl, n-octyl, isooctyl and 2 epoxytoleates. 9. Ethylhexyl ester, epoxytriacetomonolycylinic acid glyceride, tert-butylphenyl epoxystearate, 3,4 epoxycyclohexylmethanol. 10 Epoxy stearate, Epoxy stearyl benzoate, 9,10,12.13 diepoxy stearate of 3,4 epoxycyclohexylmethanol, 2-ethyl-1,3 hexa of 3,4 epoxycyclohexylcarboxylic acid - Diol esters, esters of epoxyhexahydrophthalate such as di-n-butyl, di-n-hexyl, di-2-ethylhexyl, diisooctyl, di-n-decyl, diisodecyl and n-butyldecyl, 3,4-epoxy Cyclohexylmethyl-3゜4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexanecarboxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, condensate of epichlorohydrin and bisphenol A, etc. be.

The halogen-containing resins that can be used in the present invention include polyvinyl chloride, copolymers of vinyl chloride and monomers that can be copolymerized with it, graft polymers block polymers, and comonomers such as olefins such as ethylene and propylene. saturated acid vinyl esters such as vinyl acetate, vinyl laurate, acrylic acid esters, methyl methacrylate esters, unsaturated acid alkyl esters, alkyl vinyl ethers of lauryl vinyl ether, maleic acid, acrylonitrile, styrene, methylstyrene, vinylidene chloride, (vinylidene fluoride, etc.), and polymer blends of polyvinyl chloride with, for example, acrylonitrile butadiene-styrene, methyl methacrylate-butadiene-styrene terpolymers, chlorinated polyethylene, ethylene-vinyl acetate copolymers, etc. These are halogen-containing resins such as vinyl chloride post-treated with alcohol, post-chlorinated products, etc.

The following examples demonstrate the stabilizing effect of the halogen-containing resin according to the present invention.

In the following examples, evaluation of plate-out is based on the following criteria.

No plate-out at all 1: Very slight plate-out 2: Slight plate-out 3: Obvious plate-out 4: Somewhat significant plate-out 5: Significant plate-out Forced blooming test
Comparison of blooming after soaking for 4 hours and air drying.

In the following examples, blooming was evaluated according to the following criteria.

0: No blooming at all l: Very slight blooming 2: Slight blooming 3: Obvious blooming 4: Slightly noticeable blooming 5: Significant blooming Evaluation of initial coloration and intermediate coloration is based on the following criteria.

The initial coloration here refers to the degree of coloration after 5 minutes of the gear oven test, and the intermediate coloration refers to the degree of coloration after 15 minutes.

O: Colorless 6: Brown 1: Slight yellow 7: Brown 2: Slight yellow 8: Dark brown 3: Yellow 9: Dark brown 4: Slight yellowish brown 10: Black 5: Yellow brown In the following examples, heat resistance evaluations are based on Gear It is expressed as the time (minutes) required for the sheet to darken in the oven.

Example I 100 parts by weight of PVC (P=1050), 50 parts by weight of dioctyl phthalate, 3 parts by weight of epoxidized soybean oil, 0.5 parts by weight of calcium stearate, 0 parts by weight of sink stearate
．． The exemplified compound of the present invention and the comparative example compound were added to 5 parts by weight and 1 part by weight of trisnonylphenyl phosphite, and triblended.

After mixing with a mixing roll at 170°C for 5 minutes, a 0.4 mm sheet was prepared and subjected to a gear oven test at a temperature of 180°C.

Next, several of these sheets were stacked and molded using a heating compression molding machine.
A press sheet with a thickness of 2 was produced under conditions of 0° C., 100 kg/ca, and 10 minutes.

Table 1 shows the results of heat resistance, initial coloration, intermediate coloration, plateout, and blooming.

Example 2 100 parts by weight of PVC (P=1050), 30 parts by weight of dioctyl phthalate, 20 parts by weight of dioctyl adipate,
Barium stearate, 0.5 parts by weight, zinc stearate 0.5 parts by weight, trisnonylphenyl phosphite 0.5 parts by weight, isodecylphenyl phosphite 0.5 parts by weight
The exemplified compound of the present invention and the comparative compound were added to 2 parts by weight of epoxidized soybean oil and triblended.

0.4m7 after kneading for 5 minutes in a mixing mall at 170℃
A gear oven test was conducted on a sheet of M at a temperature of 180°C.

Next, several of these sheets were stacked and heated to 170 mm using a compression molding machine.
℃-100kg/crA-10 minutes, thickness 2m7
A 1L press sheet was prepared.

The results of heat resistance, initial coloration, intermediate coloration, plateout, and blooming are shown in Table 2.

Example 3 Each of the exemplified compounds was added to 100 parts by weight of PVC (P=1050) and 2.0 parts by weight of dibutyltin dilaure, triblended, mixed on a mixing roll at 175°C for 5 minutes, and then a sheet of 0.4 mm was prepared. A gear oven test was conducted at a temperature of 180°C.

Next, several of these sheets were stacked and molded using a heating compression molding machine.
Thickness 2 under conditions of 5℃-100kg/crtt-10 minutes
A press sheet of mm was prepared.

Table 3 shows the results of initial and intermediate coloring properties, heat resistance, and plate-out.

Claims (1)

[Scope of Claims] 1. 1 of the diketo acid ester compounds represented by the following general formula:
A stabilizer composition for a halogen-containing resin, characterized by containing one or more species. General formula (where R1, R2, and R3 represent an alkyl group, an allyl group, an aryl group, an alkylaryl group, an aralkyl group, and an alkoxyalkyl group, and these may be the same or different. Also, these groups (2) The stabilizer composition according to claim 1, characterized in that ethylbenzoyl acetate is used as the diketo acid ester.