JPS62205141A - Stabilizer for use in synthetic polymeric material - Google Patents

Abstract

PURPOSE:To provide the titled stabilizer having adequate favorable effect in terms of light stability, thermal stability, and discoloration resistance, containing, as active ingredients, both piperidyl-triazine derivative and sulfur-based anti-oxidant. CONSTITUTION:The objective stabilizer containing as active ingredients, (A) at least one kind of piperidyl-triazine derivative of respective formulae I-III [X is of formula IV (R1 is H, 1-18C alkyl, etc., R2 is H, 1-18C alkyl or aralkyl), Y is morpholino, etc.; n is 2-20] and (B) at least one kind of sulfur- based antioxidant of respective formulae V-VII (R5 is 4-18C alkyl; m is 2-4; z is ethylene when m=2, of formula VIII, etc. when m=3, or of formula IX when m=4). This stabilizer is incorporated in a polymer (e.g., polyethylene, polystyrene, etc.) in an amount of 0.01-5% on a weight basis.

Description

DETAILED DESCRIPTION OF THE INVENTION (Objective) The present invention relates to a stabilizer for synthetic polymer materials, which is characterized by containing a piperidyl-triazine derivative and a sulfur-based antioxidant as active ingredients.

Synthetic materials such as polyethylene, polypropylene, vinyl chloride, and polyurethane are susceptible to deterioration due to the effects of light, heat, oxygen, and the like. To prevent these deteriorations, various light stabilizers, heat stabilizers, and antioxidants are used.

Among conventionally known photostabilizers, piperidine compounds having a 2.2.6.6-titramethylpiveridyl group as a partial structure have an excellent photostabilizing effect, but do not have sufficient thermal stabilizing effects. Therefore, the combination with various heat stabilizers has been studied, but satisfactory effects have not been obtained in terms of light stability, heat stability, and coloring resistance.

The inventors of the present application have conducted intensive studies over many years with the aim of developing a polymer stabilizer that has sufficient effects in terms of photostability, thermal stability, and coloring resistance. As a result, the piperidyl-triazine structure By combining a specific piperidine compound having The invention of the present application has been completed.

(Structure) The synthetic polymer material stabilizer of the present invention has the following general formula Cl5
The active ingredients include at least one piperidine-triazine derivative having the formulas (L) to CIC) and at least one sulfur-based antioxidant having the following general formulas (Ha) to (lc).

In the above formula, a group having Formula R has the same meaning as R2 described below. )
and R2 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an optionally substituted aralkyl group. ], Y is a morpholino group or a group having the formula -NHR4 [
In the formula, R4 is an alkyl group having 1 to 18 carbon atoms or the formula has the same meaning as described above. ), and n is 2
Indicates an integer between 20 and 20.

In the above formulas (a) to (IC), R5 represents an alkyl group having 4 to 18 carbon atoms, m represents an integer of 2 to 4, and when m is 2, 2 is an ethylene group. and when m is 3, 2 represents a group having the formula -CH-(1'H-(1'H2-) or.

In piperidyl-triazines (Ia) to (IC), the alkyl group having 1 to 18 carbon atoms represented by R1 may be linear or branched, such as methyl, ethyl, l
1l-7' lobil, isopropyl, n-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-decyl, n-dodecyl, n-octadecyl, preferably having 4 to 8 carbon atoms. Alkyl groups, e.g. n-
Butyl, n-hexyl, n-octyl, and 2-ethylhexyl.

The alkoxyalkyl group having 3 to 22 carbon atoms represented by R1 can be an alkyl group having 2 to 4 carbon atoms with an alkoxy group having 1 to 18 carbon atoms. The alkoxy moiety having 1 to 18 carbon atoms may be an alkoxy having an alkyl group as exemplified in R1 above, preferably an alkoxy having 1 to 8 carbon atoms, such as methoxy, ethoxy, n-probogyoxy, impropoxy. , n-butoxy, D-hectoxy, and n-octoxy. Alkyl moieties having 2 to 4 carbon atoms are, for example, ethyl, n-propyl, isopropyl,
It can be n-butyl, inbutyl, preferably n-propyl.

The optionally substituted aralkyl group represented by R1, R2 or R5 can be, for example, benzyl, phenethyl, p-If rubenzyl, p-chlorobenzylthea, preferably benzyl.

The alkyl group having 1 to 18 carbon atoms represented by R2, R3 or R4 may be the same as the alkyl group exemplified for R1 above.

R2 or R5 is preferably an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, In-propyl, isopropyl, n-7''yl, particularly preferably methyl, and R4 is Preferably, alkyl groups having 4 to 3 carbon atoms, such as n-butyl, t-butyl,
t-pentyl, t-octyl, particularly preferably t-pentyl, t-octyl;
-It is octyl.

The alkyl group having 4 to 18 carbon atoms represented by R5 is the same group as the alkyl group having 4 to 18 carbon atoms among the alkyl groups having 1 to 18 carbon atoms exemplified in R1 above. It is preferably an alkyl group having 10 to 18 carbon atoms.

Also, among the piperidyl-triazine derivatives, preferably:
A compound having formula (Ia) or formula (Ib), particularly preferably a group X having formula (1) in which R1 is an alkyl group having 4 to 8 carbon atoms, R2 is a hydrogen atom, A compound that is a methyl group or a benzyl group.

Examples of the compounds (Ia) to (IC) include the following compounds.

H-X 16
4-518
Among 4-5 sulfur antioxidants,
Preferred are compounds having the formula (Ha), particularly preferred are compounds in which R5 has 10 to 18 carbon atoms.

Compounds C11a) to (IC) can be specifically exemplified by the following compounds.

19 Di-lauryl thio-di-propionate 20 Di-myristyl thio-di-propionate 21 Di-stearyl thio-di-propionate 22 Glycerol Tris(3-dodecylthiopropionate) 23 Trimethylolpropane Tris(3-octadecylthiopropionate) 24 Pentaerythritol Tetrakis(3-dodecylthiopropionate) 25 3.9-hyx(2-)”f-sylthioethyl)-2
, 4,8,10-tetraoxaspiro[5°5]undecane.Synthetic polymers stabilized by this method include:

Olefin and diene polymers Homopolymers of olefins and dienes (e.g., low density, linear low density, high density and crosslinked polyethylene, polypropylene, polyisobutylene, polymethylbutene-1,
polymethylpentene-1, polyisoprene and polybutadiene), mixtures of such homopolymers (e.g.
mixtures of polypropylene and polyethylene, polypropylene and polybutene-1, or polypropylene and polyisobutylene), olefin copolymers, ethylene-propylene copolymers, propylene-butene-1 copolymers, propylene-isobutene copolymers, ethylene-butene-1 1 copolymer), and copolymers of olefins and dienes (e.g. terpolymers of ethylene and propylene with dienes such as butadiene, hexadiene, dicyclopentadiene or ethylidene norbornene): styrene polymers of polystyrene, styrene or α-methylstyrene. Copolymers (e.g. styrene-maleic anhydride copolymers, styrene-butadiene copolymers, styrene-acryloni) IJ lucopolymers, styrene-acrylonitrile-methyl methacrylate copolymers, styrene-acrylonitrile-acrylic ester copolymers, acrylic acid to provide impact strength styrene-acrylonitrile copolymers modified with ester polymers and styrene polymers modified with EPDM to provide impact strength), and graft copolymers of styrene (e.g., graft polymers of styrene to polybutadiene, usually acrylonitrile-butadiene-styrene or AE8 Graft polymers of styrene and acrylonitrile on polybutadiene (referred to as plastics) and mixtures thereof with the above styrene copolymers): vinyl halide and vinylidene polymers polyvinyl chloride, poly, vinylidene chloride, polyvinyl fluoride, polychloroprene, a-base rubber, Vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinyl acetate
copolymer, vinyl chloride-ethylene copolymer, hinichloride I)! :/-vinyl hexate copolymers: polyacrylic and polymethacrylic esters, polyacrylamides and polyacrylonitrile: polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyphthalic acid Copolymers of allyl, polymelamine allyl, and the above monomers with other types of vinyl compounds (flJ, t-ethylene-vinyl acetate copolymers): homopolymers and copolymers of vinyl compounds in epoxy polymers (e.g., polyethylene-vinyl acetate); Polymers of bisglycidyl ether compounds: polyoxymethylene, oxymethylene-ethylene oxide copolymers, polyoxyethylene, polypropylene oxide, polyisobutylene oxide and polyphenylene oxide: derived from diamines and aliphatic or aromatic dicarboxylic acids, and/or aminocarboxylic Polyamides and copolyamides derived from acids or the corresponding lactams: e.g. nylon-6
, nylon-6/6, nylon-6710, nylon-
11, Nylon 12: Polyesters derived from dicarboxylic acids and dialcohols and/or from oxyacids or their corresponding lactones: for example, polyethylene terephthalate, polybutylene terephthalate, polycyclohexane-1,4
- Dimethylene terephthalate: Crosslinked polymers Crosslinked polymers derived from aldehyde on one side and phenol, urea or melamine on the other side: For example, phenol-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins and diaryl phthalate resins: Alkyds Resins such as glycerol-phthalic acid resins and their mixtures with melamine-formaldehyde resins: unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols, using vinyl compounds as crosslinkers The obtained unsaturated polyester resin and its flame-retardant modified product by chlorination.

Compound (Ia) of the present invention necessary for effective stabilization of polymers
~(Ic) and compound (Ila) ~(IC) NoJ
ia depends on various factors, such as the type and nature of the polymer in question, its intended use, and the presence of other stabilizers. Generally, it is sufficient to use the stabilizer of the present invention at 0.001 to 5% by weight, based on the weight of the polymer, but the most effective range varies depending on the type of polymer: i.e., for olefin, diene, and styrene polymers. is 0.001% to 2.0% heavy metal, preferably 0.02% to 1.0% heavy metal.
: For vinyl chloride and vinylene polymers, α01 to 1.0, preferably 0.02 to 15
Weight %: and for polyurethane and polyamide, from 001 to 5.0, preferably from 002 to 2.
The amount of O7 is high. If desired, two or more of the stabilizers of the present invention can be used together.

The stabilizers of the present invention can be readily incorporated into the polymer by conventional techniques at any convenient stage prior to manufacturing the shaped article.

The stabilizer for polymers of the present invention can appropriately contain various additives commonly used in the field of polymer technology, such as the phenolic antioxidant 2,6-di-t-butyl. -p-cresol, stearyl-β-(4-hydroxy-3,5-di-t-butylphenyl)propionate, distearyl (4-hydroxy-3-methyl-S-butyl)penzylmalone),
12-methylenebis(4-methyl-8-t-)-f-ruphenol), 4,4-methylenebis(2,6-di-
t-butylphenol), 2,2-methylenebis[6
-(1-methylcyclohexyl)p-cresol], bis[3,3-bis(4-hydroxy-3-t-butylphenyl)butyric acidocoglycol ester, 4.
4-7' thylidene bis(6-1-butyl-m-cresol), 1.1+ 3-)lis(2-methyl-4-hydroxy-5-t-butylphenyl)butane, t, 3.
5-) Lis(3,5-di-t-7"f-4-hydroxybenzyl)-λ4.6-drimethylbenzene, 3.9
-bis[1,1-dimethyl-2-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]-2,4,8
, 10-tetraoxaspiro[5,5]undecane, tetrakis[methylene-3-(3,5-di-t-butyl-
4-Hydroxyphenyl)propionate comethane, 1
．． 3.5-) Squirrel (3,5-G-t-7” Chill-4-
hydroxybenzyl) insia slate and 1.3.5
-) Lis[3,5-di-butyl-4-hydroxyphenyl]propionyloxyethyl]isocyanate, bis[3-C3,S-di-t-butyl-4-hydroxyphenyl)propionyl]oxamide phos phyto-based stabilizers) ys(2,4-c-t-)f-ruphenyl) phosphite, triphenyl phosphite, tris(nonylphenyl) phosphite, cis-f7 lylbentaerythritol diphosphite, 4,4-butylidene bis(
3-Methyl-6-1-butylphenyl-di-tridecyl) phosphite, bis(2,4-di-t-butylphenyl)pentaerystol diphosphite □ Ultraviolet absorber 2-hydroxy-4-methoxybenzophenone, 2- Hydroxy-4-n-octoxybenzophenone, 2.4
-dihydroxybenzophenone, 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-
di-t-butylphenyl)-5-chlorogastric benztriazole, 2-(2-hydroxy-5-methylphenyl)benztriazole, 2-(2-hydroxy-3,5-di-t-amylphenyl)benzo Triazole, phenyl salicylate, λ4-di-t-butylphenyl-3.5
- Sheet t-phthyl-4-hydroxybenzoate Nickel stabilizer N1-monoethyl-3,5-di-t-butyl-4- and dibenzylphosphonate in the slurry, butylamine-Ni -
2,2-thiobis(4-1-octylferulate) complex, N1-dibutyl-dithiocarbamate, N1-λ5
- di-tert-butyl-4-hydroxybe/shade Metal salts of higher fatty acids calcium, barium, zinc, cadmium, lead or nickel stearate, calcium, cadmium, barium or zinc laurate.

If necessary, it can be used in combination with heavy metal deactivators, nucleating agents, organic tin compounds, plasticizers, epoxy compounds, pigments, fillers, foaming agents, antistatic agents, lubricants, processing aids, and the like.

Plastics stabilized in this way can be used in a wide variety of forms, for example as films, delicacies, tapes, compression molding materials, coating compositions or paints.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1゜The following formulation was placed in Prabender Plasticorder for 20 minutes.
The mixture was homogenized by kneading for 10 minutes at 0°C.

The resulting mass was rolled into a 2-3 am thick sheet in a laboratory press. A part of this sheet is heated to 260℃ using a hydraulic press machine.
Pressurized for 6 minutes, then immediately placed in cold water for 15 m
A thick sheet was obtained. From this sheet, 50X10(Is
A test piece was prepared, placed in an oven at 150°C, and the time until whitening was measured, which was used as an index of thermal stability. At the same time, the appearance of the test piece was observed with the naked eye during preparation of the test piece and after being left open at 150° C. to measure the coloring resistance.

The light stability was determined by testing the above test piece in a Sunshine Carbon Weather Meter at a blackboard temperature of 63±3°C and spraying 1
The exposed samples were exposed to light at a rate of 2 minutes/60 minutes and were periodically subjected to a tensile test, expressed as the time for elongation to fall to 50% of the initial value.

<Blend> Unstabilized polypropylene CMIFR: 1.5) 100
Heavy cod calcium stearate a10 stearyl 3-(3,5-&di-monobutyl-4-hydroxyphenyl) propionate a10 tetrayasu-[methylene-3-(&5-cyt-7'ty-4-hydroxyphenyl)propionate comethane 110 heavy cod test compound table 1 *) A: At the time of test piece creation.

B: After being opened for 4 weeks at 150°C.

■: Colorless, 0. : Almost colorless, Δ: Slightly colored, ×: Colored.

**) Photostability = 450 hours As can be seen from Table 1 above, the composition of the present invention has an excellent mutual effect on heat resistance, excellent coloring resistance, and sufficient effect on light resistance. It can be said that it has the following.

Claims (1)

[Claims] Piperidyl having the following general formulas (Ia) to (Ic)
At least one triazine derivative and the following general formula (I
A stabilizer for synthetic polymer materials, characterized in that it contains at least one of the sulfur-based antioxidants Ia) to (IIc) as an active ingredient. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( I a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( I b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( I c) Above formulas ( I a) ~ ( Ic), where X is a group having the formula ▲A mathematical formula, a chemical formula, a table, etc.▼(III) [wherein R_1 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a group having 3 to 18 carbon atoms] An alkoxyalkyl group having 22 atoms, an optionally substituted aralkyl group, or a group having the formula ▲Numerical formula, chemical formula, table, etc.▼(IV)
In the formula, R_3 has the same meaning as R_2 described below. ),
R_2 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an optionally substituted aralkyl group. ], Y is a morpholino group or a group having the formula -NHR_4 [wherein R_4 is an alkyl group having 1 to 18 carbon atoms or the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (VI) The group having (
In the formula, R_3 has the same meaning as described above. ), n
represents an integer from 2 to 20. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IIa) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IIb) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IIc) In the above formulas (IIa) to (IIc), R_5 represents an alkyl group having 4 to 18 carbon atoms, m represents an integer of 2 to 4, when m is 2, Z represents an ethylene group, and when m is 3, Z represents Formula -CH_2-CH-CH_2-
Or, it indicates a group that has the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and when m is 4, Z indicates a group that has the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼.