JPS585352A - Stabilizer for halogen-containing resin - Google Patents

Abstract

PURPOSE:To provide a stabilizer which is effective in inhibition of discoloration and improvement in weather resistance of a halogen-contg. resin and does not cause plateout or blooming, consisting of a complex compd. of a diketo ester with a GroupI-VIII metal. CONSTITUTION:The titled stabilizer consists of a complex compd. of a diketo ester of formulaI[wherein R1-3 are each alkyl alkenyl, aryl, alkoxyalkyl which may be substituted; R3 may be a group of formula II (wherein M is a GroupI-V or VIII metal; n is an integer including zero)]with a GroupI-V or VIII metal of the Periodic Table. This stabilizer can be obtd. by reacting a diketo ester with the corresponding metal oxide. 0.005-5pts.wt. said complex compd. is blended with 100pts.wt. halogen-contg. resin such as PVC or polyvinylfluoride to form a stabilized resin compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a halogen-containing resin phase stabilizer ILKQIIIK. In more detail, it has excellent color resistance, heat resistance, weather resistance, roll surface sticking phenomenon (plate-out phenomenon), and additive blow-out phenomenon (pluming phenomenon).
The present invention relates to an improved stabilizer for halogen-containing resins.

Halogen-containing resins become yellow due to photodeterioration mainly caused by ultraviolet rays after being heated during molding or becoming a processed product.
It is well known that it will no longer be possible to produce an excellent product. 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 multifaceted in addition to the above-mentioned heat and light. Conventionally used stabilizers have various characteristics in terms of their effects, and no stabilizer that is fully satisfactory has been obtained. Even though relatively good stabilizers have been put into practical use, stabilizers with even better effects are required in order to obtain even better leather products.

For example, organotin stabilizers have very good cooling effects. In particular, organic tin mercap)-based stabilizers are very effective stabilizers with excellent heat resistance and initial coloring effects, but they have a strong peculiar odor and still pose problems in terms of the working environment.

Furthermore, organic acid salts of alkaline earth metals generally have excellent heat resistance, but are poor in initial coloring properties. For example, when obtaining a colored product, it not only takes time to finely match the colors, but also the processing temperature and time may vary, making it difficult to obtain the desired uniform colored product. have.

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, making thermal processing unstable. The inventors of the present invention have conducted various studies and found that it contains seven or more complex compounds of a diketo acid ester compound represented by the following general formula and a metal element from ■ to V or ■ of the periodic table. Featured features
・Stabilizer 1 for Rodan resin \/S Xi (However, R,, R,, R, are alkyl groups, alkenyl groups,
It refers to aryl groups, alkyl groups, dialkyl groups, and those having substituents, and these groups may be the same or different. Further, Rs is K<, M is a metal element of group ① to V or ② of the periodic table, and n is an integer including O and corresponds to the valence of the metal. ) As specifically shown in the KLv example, the stabilizing effect of diketo acid esters, which have extremely excellent color resistance and weather resistance, as well as remarkable heat resistance, pluming, and plate-out phenomena, can be enhanced by adding a polishing agent. In the present invention, by forming KL into a complex compound with a specific metal, it exhibits a selective effect on halogen-containing resins. For example, even a small amount of Zn salt improves initial coloration, and ca* improves heat resistance. This slightly different selective performance plays an important role when commercializing halogen-containing resins.

In the present invention, each of the claimed complex compounds is 0.0 to halogen-containing resin/001111isK
It is preferable to use the compound in the proportion of 03-j heavy duty. The compound shown in the present invention is a complex compound and forms various compounds depending on the ligand represented by the general formula and the central metal surrounding it. An example is shown in the following table. Here, "H, R2s" Hha in the table is shown in the general formula in the claims, and the metal elements in the table are central elements of the complex compound. Further, M in R1 is similarly shown in the general formula in the claims.

These compounds can be produced by reacting a diketo acid ester with an oxide of gold or the like. Stabilizers for halogen-containing resins may be used singly, but they may also be produced by reacting raw materials at the same time to produce a mixed product (on-paok product) of multiple stabilizers.

In order to obtain the compound of the present invention using multiple raw materials (e.g., diketo acid ester, β-diketone, fatty acid, organic phosphite, epoxy compound, and metal oxide) in the manufacturing process, for example, gold 1It - A compound having a structure that becomes a salt of a diketo acid ester and a fatty acid by sandwiching the diketo acid ester and a fatty acid may be formed, and in this case also, it can be used as the composition of the present invention.

The chlorine-containing resins to be stabilized in the present invention are polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinyl bromide, polyvinylidene bromide, brominated polyethylene, brominated A homopolymer such as polyglobylene, polyvinyl fluoride, polyvinylidene fluoride, chlorinated rubber, post-chlorinated polyvinyl chloride, or a halogenated monomer that is excellent in copolymerization such as vinyl chloride,
Vinyl acetate, ethylene, globylene, styrene, inbutylene, isoprene, butadiene, methylstyrene, maleic acid, maleic ester, acrylic warm ester,
Methacrylic acid ester, acrylonitrile, vinyl laurate, laurated vinyl ether, vinylidene chloride, chlorinated ethylene.

Chlorinated globylene, vinyl bromide, vinylidene bromide.

These include multidimensional co-electrochemical combinations with vinyl heptatide, vinylidene fluoride, etc. arbitrarily selected at least one polymer, and polymer blends of these with each other or with other polymers.

The stabilizer of the present invention may be supplemented with one or more other commonly used stabilizers or additives. These include, for example, plasticizers, organic phosphites, organic phosphates, VA tin compounds, organic or inorganic antimony compounds, organic or inorganic titanium compounds, metal soaps, epoxy compounds, ultraviolet absorbers, antioxidants, and viscosity adjusters. agents, pigments, dyes, processing aids, impact reinforcement agents, deafening agents,
Surface treatment agent, antibacterial agent, optical brightener, antifogging agent.

Dropless agents, droplet agents, antistatic agents, polyhydric or higher alcohols, saturated and unsaturated fatty acids with linear or side chains, other organic solvents, lubricants, fillers, flame retardants.

These include fragrances, organic compounds or their salts, cross-linking agents and plate-out inhibitors.

Among the above, specific examples of the organic phosphite include triphenyl phosphite, trisnonylphenyl phosphite, and tricresyl phosphite.

Triisooctyl phosphite, tridecyl phosphite, trichoethylhexyl phosphite, tridecyl phosphite, tri(octyl7enyl) phosphite, tricyclohexyl phenyl phosphite, triscyclohexyl phosphite, tridecyl Thiophosphite, triindecyl thiophosphite, phenyl di-ethylhexyl phosphite% phenyl diindecyl phosphite, phenyl dicyclohexyl phosphite, phenyl diisooctyl phosphite, phenyl di(tridecyl) phosphite , phenyl dicyclohexyl phosphite.

diphenyl isooctyl phosphite, diphenyl
Coethylhegylphosphite, diphenyl indecyl phosphite, diphenyl phosphite, diphenyl cyclohexyl phenyl phosphite, diphenyl-tridecyl thiophosphite, nonylphenyl di(
tridecyl) phosphite, phenyl p-tert-butyl dodecyl phosphite, diisopropyl phosphite, monoisopropyl phosphite, didodecyl phosphite, diyne octyl phosphite, monoin octyl phosphite, didodecyl phosphite, monododecyl phosphite Phite, dicyclohexyl phosphite, monocyclohexyl phosphite, dicyclohexyl phenyl phosphite, monodicyclohexyl phenyl phosphite, di(p-tert-butylphenyl)
Phosphite, tetra(tridecyl)-41,1-butylidenebis(-1-tertiarybutyl-3-methylphenyl)diphosphite, tetraisooctyl [Dow 4
11-thiobis(coater-butyl-!-methylphenol)] diphosphite, tetranonylphenyl polyglobylene glycol-thiphosphite, /
, /, J -) Lis [(co1-methyluda-ditridecylphosphite-5-tert-butyl) phenylcobutane, *, 47-impropylidene diphenol alkyl ('11-C11) phosphite, tetra(tridecyl ] Diglobylene glycol diphos 7-ite, tetratridecyl-*, l-impropylidenecyclohexyl diphosphite, pentakis (nonylphenyl) bisvoliptetrapyrene glyfur triphosphite, heptakis (nonylphenyl) y-) lakis polypropylene glycol pentaphosphite, heptakis(nonylphenyl]tetrakis(bisphenol A)penta-1 phosphite, decakis(nonylphenyl)hephtakis(diglobylene glycol)octaphosphite, decafenylhebutadipropylene glycol octaphosphite,
Tetrakis(inoctoxycarbomethylenethio)l,
cooxycarbonylmethylenethioethylene diphosphite, dibutoxycarboethylenethio (pentaerythritol tetrathioglycol fudiphosphite, diine octoxycarbomethylenethio (pentaerythritol tetrathioglycol) diphosphite, tetrakis (mercaptrauryl) 1,2-dimercapto -Ethylene diphosphite, tetrakis (mercaptrauryl)
/, 1-dimercapto-hexylene diphosphite, tetrakis(mercaptroururine β, βI-dimercapto-ethyl ether diphosphite, pentakis(dodecyl-mercapto)bis(l,6-hexylene dimercapto)triphosphite , tris(co,q-tert-butylphenyl) phosphite, l, $1-butylidene bis(J-methyl-6-tert-butylphenyl-di-dodecyl) phosphite, water m-tei, #1
-Impropylidene diphenol phosphite, coater-tertiary-butyl-α (J-tertiary-butyl-α)
hydroxyphenyl) p-11 nyl bis(p-nonylphenyl) phosphite, ri, ri 1-butylidene bis(3
-Methyl-〇-tert-butylphenyl ditridecyl phosphite, distearyl pentaerythritol diphosphite, tricyclohexylphenyl phosphite, tridodecyl mercapto phosphite, decaffenyl heptadipropylene glycol octaphosphite,
These include dibutylpentaerythritol diphosphite, didecylpentaerythritol diphosphite, and dioctylpentaerythritol diphosphite.

Specific examples of organic phosphate esters include nonylphenoxypolyethoxyphosphoric acid, tridecylhydroxypolyethoxyphosphoric acid, octyloxypolyethoxyphosphoric acid, lauryloxypolyethoxyphosphoric acid, stearyloxypolyethoxyphosphoric acid, and oleyloxypolyethoxyphosphoric acid. ethoxylic acid,
These include tertiary-butylphenoxypolyethoxyphosphoric acid, octylphenoxypolyethoxyphosphoric acid, dinonylphenoxypolyethoxyphosphoric acid, and dodecylphenoxypolyethoxyphosphoric acid.

Specific examples of organic tin compounds include mono(or di)methyltin tris(or bis(in-octylthioglycolate)), mono(or di)octyltin tris(or bis)(in-octylthioglycolate), (or ji)
Butyltin tris(or bis)(inoctylthioglyflate), mono(or di)methyltintris(or di)
Laurate, mono(or di)butyltintri(or di)
Laurate, mono(or di)octyltintris(or di)laurate, mono(or di)methyltintris(or bis)(inoctylmalate), mono(or dibutyltintris(or bis)(in) octyl malate)
, mono(or di)octyltin tris(or bis)(inoctylmalate), mono(or di)methyltin tris(or bis)(comelkabutethyl oleate), mono(or di)methyltin tris(or di) oleate, mono(or di)alkyl(0,~1.)tin sulfide,
Mono (or bis) (butyl acrylate°) tin tris (
or bis) (1 so-octylthiog IJ flat), mono (or bis) (methyl acrylate) tin tris (also habis) (in-octyl thioglycolate), mono (or di) alkyl (o, -,) su, t:t *'r-ide, mono(or di)methyltin maletopo 1Jmer, mono(or di)butyltin maletopo 17mer, mono(or di)octyltin maletopo 17mer, mono(or di)alkyl(a) ,~1.) tin-β-mercaptopropionate, mono(or di)alkyl(0,~4.)tin thioglyflate, mono(or di)alkyl(C,~,2) tin IF (also di)mercaptoethanol, mono(or di)alkyl (C4-1.) tin tri(or di)lysyllate, mono(or di)alkyl (0, to, 2) tin tri(or di)oleate.

In particular, these include organic tin compounds shown in Publications Nos. 1 and 2.

Specific examples of organic or inorganic antimony compounds include tris(in-octyl thioglycolate co-antimony, monobutyl antimony bis(in-octyl thioglycolate), dibutyl antimony mono(in-octyl thioglycolate), tris(J-mercagt), antimony (ethyl oleate), antimony trioxide, etc.

Examples of organic titanium compounds include tetrasder IJ rutitanate and tetrakis (coethylhexyl titanate).
, inglobyl inostearyl titanate, diimpropoxybis(acetylacetone)titanate, triptoxymonostearyltitanate, dihydroxybis(lactiacide)titanate, inpropyltridecylbenzenesulfonyltitanate, inpropyltris(
Dioctyl pyrophosphate) titanate, Tetraisopropyl bis(dioctyl phosphite) titanate, Tetraoctyl bis(ditridecyl phosphite) titanate, Tetra(co-diallyloxymethyl-noptyl) bis(cytoI-nodecyl) phosphite titanate, Bis (dioctyl pyrophosphate) oxyacetate titanate), ) lith(dioctyl/<ylophosphate) ethylene titanate, (mono or di)butyl titanium (tri or di) laurate, (mono or di) butyl titanium (tris or bis) in octyl These include thioglycolate, tetrakis(in-octylthioglycolate) titanium, tetrakis(todecylmercaptoate) titanium, and titanium dioxide.

゛ Specific examples of metal soaps include saturated and unsaturated soaps with linear or side chains of 115 titanium, sodium, potassium, magnesium, calcium, strontium, zinc, cadmium, aluminum, tin, and lead. acid salts, aromatic carboxylic acid salts, polyvalent carboxylic acid salts,
and 111 or more selected organic acid salts, fatty groups, neutral salts, and basic salts of these acids with substituents t-W.
Examples of the organic acids include 3-3o unsubstituted, substituted, saturated, unsaturated aliphatic or aromatic carboxylic acids, caproic acid% heptanoic acid, coethylhequinic acid, undecane. Acid, lauric acid, neoto-fudecanoic acid, f-listic acid, pentadecanoic acid, N\\'s ugly cypal-acid acid, hebetadecanoic acid, stearic acid, hydroxystearic acid, dihydroxystearic acid, tonadecanoic acid, aranic acid, Heneicosanoic acid, behenic acid, tricosanoic acid, lignoceric acid, bentafsanic acid, montan I! , nonacosanoic acid, melisic acid, hentriacotanoic acid, 31 synthetic mixed odd-numbered acids derived from α-olefins and starting from 1 to 1 carbon atoms, oleic acid, ricinoleic acid, acrylic acid, linuric acid, linoleic acid, crotonic acid, Aliphatic carboxylic acids such as acetoacetic acid, isostearic acid, inoctylic acid, neoacid, octylic acid, etc.; dibasic acids such as malonic acid, adipic acid, azelaic acid, sepatic acid, 7-taric acid, thiodipropionic acid, dithiopropionic acid, etc. Acids and these two bases, substituted or unsubstituted alkyl alkoxy alcohols with linear or side chains having 7 to 8 carbon atoms, and 3 to 11 carbon atoms.
1 Schifky alkyl, aryl alcohol, aryl, alkylaryl alcohol, etc. 0 * 1 ester,
Benzoic acid, methylbenzoic acid, butylbenzoic acid, benzoylbenzoic acid, phenylacetic acid, salicylic acid, fumaric acid,
Cyclic acids such as naphthoic acid, na7talic acid, abietic acid, dihydroabietic acid, phenylstearic acid, pyrrolidonecarboxylic acid, cinnamic acid, p-tert-butylbenzoic acid, rosin acid, naphthenic acid, dehydroacetic acid, etc. Examples include organic acids such as nonylphenol, octylphenol, t-butylphenol, and acetoacetate.

Specific examples of epoxy compounds include epoxidized soybean oil,
Epoxidized linseed oil, epoxidized tallow oil, epoxidized tallow oil, epoxidized cottonseed oil, epoxidized seven-leaf oil, epoxidized whale oil, epoxidized tall oil, epoxidized sunflower oil, epoxidized fish oil, diacetate of epoxidized soybean oil Monoglycerides, epoxidized diacetomonoolein, benzoyl distearate, butyl epoxy stearate, cyclohexyl epoxy stearate, dihydrononyl epoxy stearate, epoxy stearate.

coethylbutyl esterate, methoxyethyl epoxystearate, inodecyl epoxystearate.

Inoctyl epoxystearate, tetrahydrofuryl epoxystearate, phenyl epoxystearate, diethyl in acetate distearate, butyl epoxytol oil, n-octyl, inoctyl>X
3. tert-butylphenyl epoxy stearate, epoxy triacetomonolysyl acid glyceride, tert-butylphenyl epoxy stearate, 3. Of eboxycyclohexylmethanol! , 10-epoxy stearate, epoxy stearyl benzoate % Je'-epoxy shift tetrahexyl methanol 9,10. /Ko.

/J-Jepoxystearate %'t''-coethyl of epoxycyclohexylcarboxylic acid-/, J-
Hex't-diol ester, esters of epoxyhexahydrophthalic acid such as di-n-butyl, di-n-hexyl, di-ethylhexyl, diisooctyl, di-n-decyl, diisodecyl and n-butyldecyl; 3.
Terepoxycyclohexylmethyl-3,4I-diboΦ
Cyclohexanecarboxylate, J, 41-epoxy-1-methylcyclohexanecarboxylate,
Bis(J,41-epoxy-6-methylcyclohexylmethyl)adipate, a condensate of epichlorohydrin and bisphenol A, and the like.

Specific examples of processing aids and impact reinforcement agents include chlorinated polyethylene and ethylene propylene copolymers.

Ethylene vinyl acetate copolymer, styrene butadiene copolymer, acrylonitrile styrene copolymer.

Acrylonitrile butadiene styrene copolymer.

Examples include acrylic acid ester butadiene styrene copolymer, methacrylic acid ester butadiene styrene copolymer, polystyrene, and acrylic resin.

Specific examples of lubricants include polyethylene wax, petroleum- or coal-derived paraffin wax.

Contains higher fats*, higher alcohols, natural or synthetic polymer ester waxes, ethylene bisstearoa, and other cleansers than the metal soaps mentioned above! ! :t-, such as metal salts.

Examples of fillers include oxides, hydroxides, chlorides, sulfides, carbonates, salts of II, sulfites, phosphates, and phosphites of metals in groups I to ■ or ■ of the periodic table. , silicates, nitrates, nitrites, and halates can also be used together. Specific examples include calcium carbonate, calcium oxide, calcium hydroxide, zinc oxide, zinc chloride, zinc hydroxide, zinc carbonate, and zinc sulfide. , zinc phosphite, zinc oxalate, magnesium oxide,
Magnesium hydroxide, magnesium carbonate, aluminum oxide, aluminum hydroxide, alumina, sodium silicate, aluminum silicate, magnesium silicate, calcium silicate, silicic acid metal salts such as zeolite, activated clay,
Merck, clay, red iron, asbestos, antimony trioxide, hydroxide, barium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium sulfate, etc.

Specific examples of organic compounds or their salts include:

Cophenylindole, diphenylthiourea, heptyl and stearyl β-aminocrotonic acid ester, /, J
and/or nitrogen-containing compounds such as 41-butanediol bis β-aminocrotonic acid ester, thiodiethylene glycol bis β-aminocrotonic acid ester 1-incyanuric acid and its derivatives, such as tris(2-hydroxyethyl) cyanurate, pentaerythritol, mannitol, Polyhydric alcohols such as nrubitol, carboxylic acids such as benzoic acid, methylbenzoic acid, linoleic acid, maleic acid, cinnamic acid, p-tert-butylbenzoic acid, crotonic acid, boric acid esters, thiodiglycol warm esters, acetylacetone, β-diketones and their metal salts such as benzoylmethane and benzoylacetone, acetoacetate, diketoate ester, dehydroacetic acid or its ester or metal salt, pentaerythritol tetrakis (mercaptopropionetone), pentaerythritol tetrakis (mercaptoacetate), Dicyandiamide, tannin, schellaic acid ester, malonic acid ester, λ-(
31-Methoxy-4<1-hydroxy722)indole, thiodipropionic acid esters such as dilaurylthiodiglobionate, distearylthiodipropionate, 4-anilino-/, J, j-triazinico, 4I
-dithiol, -butyl ano/, J,! -) Lyazine-λ, q-dithiol melamine, Komel Kabutoethyl oleate.

These include octylthioglycolate, -monomercabutoethanol, β-mercagutoglobionic acid, thioglycolic acid, and hexamethylenetetramine.

Next, the stabilizing effect of the halogen-containing resin of the present invention KL in Example KZ9 will be shown.

In the practical examples below, the plate-out evaluation is based on the following criteria:

0 No nibrate out at all L: Very slight great out J: Slight plate out 3: Obvious plate out 41: Moderate or significant plate out S: Significant plate out The evaluation of initial coloring, mid-term coloring, and heat resistance is as follows. It follows the standards. The initial coloring here refers to the degree of coloring after 3 minutes of the gear open test, and the degree of coloring after 1 ets of intermediate coloring.

O: Colorless 1: Brown color ／：Extreme yellow F：Brown brown Koni slight yellow G: Dark brown 3: Yellow Color Drop: Blackish brown Mite slightly yellowish brown 10: Black color S: yellowish brown Heat resistance indicates the time required to reach black color.

The evaluation of the pluming phenomenon is based on the following criteria. (Evaluation after watering and air-drying sample t-λ) O: No pluming at all 1: Very slight pluming Slight pluming 3: Obvious plumping Mites Somewhat significant pluming 5: Significant pluming Weather resistance For evaluation, UV irradiation was performed using a weather meter, and the time taken until the L9 sample began to deteriorate was observed.

Example 1 Add the exemplified compounds to the basic formulation below and dry blend.
0.41- after mixing for S minutes with a mixing roll at 5°C
Create a sheet for your friends. Each sheet piece was subjected to a gear open test under lSO''CO conditions.

Basic blend PVO (P=1030) 100 weight tm
Dioctyl phthalate 50 l Epoxidized soybean oil l Calcium stearate 0. ! I #Zinc Stearate o, sttNext, several of these roll sheets were stacked and heated in a compression molding machine/fu! "C-/001
Press sheets of thickness C and O were prepared under conditions of 9/cts2-/0 minutes.The results of heat resistance, initial coloring, mid-term coloring, pluming, weather resistance, and plate-out are shown in Table 1. Shown below.

Table I - 1st Example By adding the exemplified compounds to the following basic formulation and tri-blending/
? After mixing for S minutes with a mixing roll at j℃, a sheet of 0, *■ was created. Next, perform a gear open test on each sheet piece under the conditions of /lgC.

Basic combination pva (p=ioso) 10ottsM
13B, 10N888

J #Dioctyltin bis(-monoethylhegycyl malate ester) O, CO l Calcium stearate 0.31 Zinc stearate
0.5N Subsequently, several sheets of this roll sheet were piled up and t t soc −/
o oKp/cym2- t Thickness ko, O
Created a press sheet for X and made a friend. At this time, the results of heat resistance, initial coloring, mid-term coloring, weather resistance, and plate-out
Shown in -*-.

Claims (1)

[Scope of Claims] Contains one or more complex metals of a diketo acid ester compound represented by the following general formula and a metal element of Groups IV or I of the Periodic Table. Stabilizer for halogen-containing resins. - (However, R,, R,, R, t! Indicates an alkyl group, an alkenyl group, an aryl group, an alfukidialkyl group, and those having a substituent on these groups. L, R8 is 0 〇〇〇, but it shows the metal element of the M -Seken discipline I ~ V or VM tribe, and N corresponds to the atomic price of metal with an integer containing O1.
1