JPS6348342A - Stabilizer for synthetic high-molecular material - Google Patents

Abstract

PURPOSE:To improve the compatibility with high-molecular compds. without detriment to the light stabilization effect inherent to piperidine compds. by adding an org. carboxylic acid to a piperidine compd. as a stabilizer for synthetic high-molecular materials. CONSTITUTION:This stabilizer for synthetic high-molecular materials is com posed of at least one member selected from among piperidine compds. of formu las I, II, III and IV and at least one org. carboxylic acid active ingredients. In formulas I-IV, R' is a member selected from the group consisting of H, methyl, benzyl, acetyl groups etc.; n is an integer of 1-4; when n is 1, R<2> is a group having a -COR<5> group (wherein R<5> is member selected from the group consisting of a 1-20C alkylene group, etc.); when n is 2, R<2> is a member selected from the group consisting of a group having a -CO-R<7>-CO group, etc., (wherein R<7> is a member selected from the group consisting of a 1-20C alkylene group, etc.), when n is 3, R<2> is a member selected from the group consisting of an aliph. or arom. triacyl group, etc.; when n is 4, R<2> is an aliph. or arom, tetraacyl group; R<3> is a 1-18C alkyl group; and R<4> is a group of formula V (wherein R<1> and R<2> are as defined above). As the org. carboxylic acid, di- or tetra- carboxylic acids are preferred.

Description

DETAILED DESCRIPTION OF THE INVENTION
- It relates to a stabilizer for synthetic polymers, characterized in that it is an active ingredient.

2, 2 in the following formula (la, l to (Id, l')
．． It is well known that 6,6-titramethylpiveridine compounds are excellent light stabilizers for synthetic polymer compounds such as polyolefins.

However, depending on the combination of the piperidine compound and the synthetic polymer compound, the compatibility between the piperidine compound and the synthetic molecular compound may not necessarily be good. In such cases.

Plumes (bleed) may occur if synthetic polymer processed products containing piperidine compounds are used for a long period of time.

Such phenomena may cause problems such as stains, contamination, and decreased transparency.
impairs practicality. In particular, when a synthetic polymer is used as an agricultural film, a decrease in transparency brings about practical disadvantages.

In order to improve the compatibility between a piperidine compound and a synthetic polymer compound, the present inventors have conducted intensive studies over many years, and as a result, by adding an organic carboxylic acid to a piperidine compound.

without compromising the photostabilizing effect of piperidine compounds.

The present invention was completed by discovering that the compatibility with polymer compounds could be completely improved.〇 (Structure) The stabilizer for synthetic polymers of the present invention has the following general formulas (Ia) to (I(1)). The active ingredients are at least one type of piperidine compound having the formula ' and at least one type of organic carboxylic acid.

In the above formula, R1 represents a hydrogen atom, a methyl group, a benzyl group, and all groups, nVi represents an integer from 1 to 4, and when n is 1, R2 represents the formula -〇〇! (Group having 5 [in the formula, p and 5 are an alkyl group having 1 to 17 carbon atoms, an alkenyl group having 2 to 4 carbon atoms (in the formula, R+ has the same meaning as described above, and R6
represents an alkyl group having 1 to 8 carbon atoms. ;

], where n is 2, R2 is a group having the formula -〇〇-R'-Co- (wherein R is an alkylene group having 1 to 20 carbon atoms, and 5 to 20 carbon atoms); 9. A group in which one acyl group has the formula -OR"i (in the formula,
R5 has the same meaning as described below. An aliphatic or aromatic triazyl group or two acyl groups forming an ester bond together with a group having the formula -0R3i (in the formula, R5 has the same meaning as described below) form an ester bond. When n is 3, R2 is an aliphatic or aromatic triazyl group or a group in which one acyl group has the formula -0R3 (wherein R3 is the one described below) Indicates an aliphatic or aromatic tetraacyl group forming an ester bond with

When n is 4, R2 represents an aliphatic or aromatic tetraacyl group, and R3 is an alkyl group having 1 to 18 carbon atoms (in the formula,
R1 and R5 have the same meanings as described above. )show.

The alkyl group having 1 to 17 carbon atoms represented by R5 may be straight chain or branched, for example, methyl, ethyl, n
-propyl, isopropyl, n-7'thyl, n-hexyl, n-octyl, 2-ethylhexyl, n-decyl,
It may be n-dodecyl, n-octadecyl, preferably an alkyl group having 4 to 8 carbon atoms, such as n-butyl, n-hexyl, ni-octyl, 2-ethylhexyl.

a group 1d of alkeni having 2 to 4 carbon atoms represented by R;
Examples include tij, vinyl, froben-2-yl, 1-propenyl, 1-butenyl, preferably vinyl, propen-2-yl. or.

The group having the formula -0OR is preferably octadecaIJI
'1 is a group that does.

The alkyl group having 1 to 8 carbon atoms represented by R6 may be an alkyl group having 1 to 8 carbon atoms among the alkyl groups having 1 to 17 carbon atoms represented by R, preferably 3 to 8 carbon atoms. 6
number of alkyl groups.

The alkylene group having 1 to 20 carbon atoms represented by R7 may be linear or branched, and includes, for example, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, hebutamethylene, octamethylene, nonamethylene, decamethylene, dodecamethylene, etc. methylene, tetradecamethylene, hexadecamethylene, octadecamethylene,
It may be eicosamethylene, preferably having 4 to 1 carbon atoms.
0 alkylene groups, such as tetramethylene, hexamethylene, octamethylene, decamethylene.

R7 is a cycloalkylene group having 5 to 1 carbon atoms, 91
Step 1 can be obtained with 1.3-cyclopentalene, 1.2-cyclohexalene, 1.3-cyclohexalene, 1.4-cyclohexalene, 1.3-cycloheptalene,
Preferably it is a cyclopentalene group.

Further, a group having the formula -CO-R'-CO-y< is preferably.

Formula -co-(ca2)4-ca-, -Co-(ca2)
5-co-, -CO-(CH2)6-CO-, -CO(
C)! 2) 7-CO-, -CO-(CH2)8-(ca
2) It is a group having 2-co-.

R2 is an aliphatic or aromatic triazyl group.

For example, propane-1,2,3-toIJcarbonyl, butane-1,2,3-)υcarbonyl, butene-1゜2,
3-) tricarbonyl, trimethylamine-tricarbonyl, benzene-1,2,4-tricarbonyl, preferably propane-1,2,3-tricarbonyl, butane-1,2,3- )licarbonyl or butene-1
,2,3-tricarbonyl.

The aliphatic or aromatic tetraacyl group of R2 is, for example,
Butane-1,2,3,4-tetracarbonyl, ethylenediamine-tetracarbonyl, benzene-1,2,4,
5-tetracarbonyl, preferably butane-1
, 2,3,4-tetracarbonyl.

The alkyl group having 1 to 18 carbon atoms in R5 may be the same group as the alkyl group having 1 to 17 carbon atoms in R5 or an octadecyl group, and is preferably an alkyl group having 8 to 14 carbon atoms. .

Examples of organic carboxylic acids that are active ingredients of the present invention include acetic acid, propionic acid, butyric acid, off-white acid, benzoic acid,
aliphatic or aromatic monocarboxylic acids such as salicylic acid (preferably aliphatic carboxylic acids having 2 to 5 carbon atoms;
For example, acetic acid, propionic acid, butyric acid. Low; silicic acid, malonic acid, succinic acid, glutaric acid, adipic acid,
aliphatic or aromatic dicarboxylic acids (preferred includes aliphatic dicarboxylic acids having 6 to 14 carbon atoms, such as
These include adipic acid, sebacic acid, decane-1,10-dicarboxylic acid, and the like. ); Prono-1,2,3-tricarboxylic acid, butane-1,2,3-tricarboxylic acid, butene-1,2,3-tricarboxylic acid, nitrilotricarboxylic acid, trimellitic acid, etc. aliphatic or aromatic tricarboxylic acids (preferably propane-1,2°3-tricarboxylic acid, butane-1,2,
It is an aliphatic tricarboxylic acid such as 3-tricarboxylic acid.

];] Butane-12.3.4-tetracarboxylic acid, ethane-1,1,2,2-tetracarboxylic acid, ethylenediaminetetraacetic acid, pyromellitic acid and other aliphatic or Aromatic tetracarboxylic acids (preferably aromatic tetracarboxylic acids such as pyromellitic acid); pentacarboxylic acids such as pentacarboxybenzene; or triethylenetetramine-N,
It can be an aliphatic or aromatic hexacarboxylic acid which may contain a nitrogen atom, such as N,N-1N-2N-3N-hexaacetic acid, mellitectic acid, preferably a di- or tetra-carboxylic acid. be.

Examples of piperidine compounds having the compound (Id)'!r include the following compounds.

(□゛.H,, (I°) 1-1 1 H-COCH53//
-/ C0C3H
74n H-COC7F (+55
// −/ −COC
16H576, /-CH5// 7 // H-co-@)1G ・/
H-CO-(CI(2)2-CO-” ”
I-Co(CH2)4-Co-12〃
〆l -CO-(C[(2)8-C
O-13#-()i, i/ 14 ・ノ H-0C((Giant Σ:)
-CO-Hs 24 〃 -CH3//27
To HC8, 7 28 CH5 // 30 H-CI2 H2531CHA
-C,2H2532-COCH57 33HC4H9 34CJ 1t 35 HC8H,.

36 C [(5// Shi - - Tsuyoshi 1 bow - - n-shi □ - □ - Ikko Kaeko Issei 1-1 - ■ - - i ■ ■ - - - -, -2 □ 1. Yu 37
HCaHq 38 C84// 39 HC3H,7 40 no CI2 H
25 Among the compounds represented by formulas (Ia) to (Id)', compounds represented by formula (Ia)' are preferred, and 2.2.6.6-tetramethyl-4- is particularly preferred. Benzoylpiperidine, bis(2,2,6,6-tetramethylbiperidin-4-yl) hexanate, 1-(2-(3
,5-di-tert-butyl-4-hydroxyphenylpropionyloxy)ethyl]-4-(3,S-di-tert-butyl-4-hydroxyphenylpropionyloxy) -
2,2,6,6-titramethylbiperidia.

Examples of organic carboxylic acids include the following compounds.

41 Adipic acid 42 Sebacic acid 43 Decane-1,10-dicarboxylic acid 44
Dodecane-1,12-dicarboxylic acid 45 Propane-1,2,3-)licarboxylic acid 46 Butane-
1,2,3,4-Tetracarboxylic acid 47 Terephthalic acid 4B Trimellitic acid 49
Pyromellitic acid Synthetic polymers stabilized by this method include:

Homopolymers of olefins and dienes (e.g., low-density, low-visibility, high-density and cross-linked polyethylene, polypropylene, polyimbutylene, polymethyl)゛Ten-1
．． Polymethylpentene-1. Polyisoprene and Bo +]
butadiene).

Mixtures of such homopolymers (e.g. polypropylene and polyethylene, polypropylene and polybutene-1)
, or a mixture of polypropylene and polyisobutylene],
Copolymers of olefins (e.g. ethylene-propylene copolymer, propylene-butene-1 copolymer, propylene-isobutene copolymer, ethylene-butene-1 copolymer) and copolymers of olefins and dienes (e.g. ethylene and propylene with butadiene, hexadiene , dicyclopentadiene or ethylidene norbornene] copolymers of polystyrene, styrene or alpha-methylstyrene (e.g. styrene-maleic anhydride copolymers, styrene-butadiene copolymers, styrene-
Acrylonitrile copolymer, styrene-acrylonitrile-methyl methacrylate copolymer, styrene-
Acrylonitrile-acrylic ester copolymer,
Styrene-acrylonitrile copolymer, modified with acrylic ester polymer to provide impact strength
and styrene polymers 9 modified with EPDM to give a strong V Graft polymers of styrene and acronitrile and mixtures thereof with the above styrene copolymers): polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene,! Raw rubber, ffl
Vinyl chloride-vinyritine chloride copolymer, vinyl chloride-
Vinyl acetate copolymers, vinyl chloride-ethylene copolymers, hnyritene chloride-vinyl acetate copolymers: Polymers of α,7y-unsaturated acids and their derivatives Polyacrylic esters and polymethacrylic esters, polyacrylamides and polyacrylonitrile: Polyvinyl alcohol, polyvinyl acetate , polyvinyl stearate, polyvinyl benzoate.

Polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine, and copolymers of the above monomers with other vinyl compounds (e.g., ethylene-vinyl acetate copolymers): Epoxy polymers Homopolymers and copolymers of epoxy compounds (e.g. polyethylene oxide) and 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 derived from aminocarboxylic acids or the corresponding lactams: e.g. nylon-6,
Nylon-6/6, Nylon-6/10, Nylon-1
1. Nylon 12: Polyesters derived from dicarboxylic acids and dialcohols and/or from oxyacids or their corresponding lactones: e.g. polyethylene terephthalate, polybutylene terephthalate, polycyclohexane-1,4
- dimethylene terephthalate: crosslinked polymers derived from an aldehyde on the one hand and a 7-enol, urea or melamine on the other hand: for example phenol-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins and diaryl phthalate resins; For example, glycerol-phthalate resins and their mixtures with melamine-formaldehyde resins: unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols, obtained using vinyl compounds as crosslinkers; unsaturated polyester resin, and its chlorinated, flame-retardant modified resin.

The compounds of the present invention (Id) and organic carboxylic acids necessary for effective stabilization of corner molecules and improvement of blooming properties are determined by various factors, such as the type and quality of the target IJ mer, its It depends on the purpose of use and the presence of other stabilizers.Usually, the amount of each of the uninvented compounds (la) to (Id) and the organic carboxylic acid is 0 based on the weight of the polymer.
01 to 5% by weight is sufficient, but the most effective range varies depending on the class of the polymer: DtJ, 001 to 2.0% by weight for olefin, diene and styrene polymers, preferably 002 to 1.0iJJi
k%: 001 to 1.0 weight ratio for vinyl chloride and vinyl chloride tin polymers, preferably 0.02 to 0
．． 5% by weight: and for polyurethanes and polyamides an amount of 001 to 5.07I, preferably 0.0
2 to 2.0 weight. If desired, two or more of the compounds of the present invention and organic carboxylic acids can be used together.

The compounds (Ia) to (Id) of the invention and the organic carboxylic acids can be readily incorporated into the madder molecules 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 cooling agents commonly used in the field of polymer technology, such as 2,6-di-t-butyl-p-cresol. , stearyl-β-(4-hydroxy-3,5-di-t-butylphenyl)propionate, distearyl(4-hydroxy-3-methyl-5-z-butyl)benzylmalonate%
2.2'-methylenebis(4-methyl-6-Z-butylphenol), 4.4'-methylenebis(2,6-di-t-)' methylphenol, 2.2'-methylenebis[6-[1- methylcyclohexyl) p-cresol]
.

bis[3,3-bis(4-hydroxy-3-1-butylphenyl)butyric acid coglycol ester,
4.4'-7'f IJ fnhix (6-z-butyl-m-cresol), 1.1.3-tris(2-methyl-4-hydroxy-5-t-butylphenylsibutane, 1 ,3,5-tris(3,5-di-1-butyl-4
-Hydroxybenzyl) -2゜4,6-)rifthylbenzene. 3,9-bis[1,1-dimethyl-2-(3,
5-di-t-butyl-4-hydroxyphenyldiethyl) -2,4,8,10-tetraoxaspiro C5,5
] Urantican tetrakis [methylene-3-(3,5-
G-t-].

thyl-4-hydroxyphenyl]propionate]methane, 1.3.5-)lith(3,5-di-monobutyl-4-hydroxybenzylline cyanurate,
．． 5-) Squirrel [3,5-jeep fk-4-hi)'
Roxyphenyl]propionyloxyethyl]in cyanurate, bis[3-(3,5-di-t-butyl-4-
hydroxyphenyl)propionyl]oxamide phosphite stabilizers tris(2,4-di-t-butylphenyl) phosphite, triphenyl phosphite, tris(nonylphenyl diphosphite, distea-11-rupentaerythritol diphosphite).

4.4'-Butylidene bis(3-methyl-6-1-butylphenyl ditritecylinophosphite, bis(2
,4-di-t-butylphenyl]pentaerythol
Diphosphite 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2.4
-dihydroxybenzophenone, 2-(2'-hydroxy-3'-1-butyl-5'-methylphenyl)-5-
Chloropenttriazole, 2-(2'-hydroxy-
3/, S/-G t-butylphenyl)-5-
Chlorobenztriazole, 2-(2'-hydroxy-51-methyA, 7Z=L)hensotriazole, 2-(2'-hydroxy-3', 5'-sheet t-
Amylphenyl] penz° triazole, phenyl salicylate.

2.4-di-t-butylphenyl-3,5-di-monophthyl-4-hydroxybenzoate Nickel stabilizer N1-monoethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, butylamine-Ni −z
, f-thiobis(4-1-octylfert) complex,
N1-dibutyl-dithiocarbamate, N1-15-
Di-t-butyl-4-hydroxybenzoate Higher fatty acid metal salts 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, etc. .

It can be used as a tape, compression molding material, coating composition or paint.

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

Example 1 Unstabilized linear low density polyethylene (MFR~2.
O) 100 parts, octadecyl 3- as an antioxidant
0.1 part of (3,5-di-tert-butyl-4-hydroxyphenyl)propionate and the stabilizers of the invention shown in Table 1 were homogenized in a Brabender plasticorder at 200 DEG C. for 10 minutes. The resulting mass was rolled into plates with a thickness of 2-31 in a press. A part of this plate is pressed into a press.
Pressure was applied at 80° C. for 6 minutes, and then immediately placed in cold water to obtain a sheet with a thickness of 0.5 mm. By a similar method, 0.
A 0.1 mm thick film was formed from a 5 rm thick sheet. This film was cut into 50 x 120 mm O specimens.

This test piece was irradiated with light in a Sunshine Carbon Weathermeter at a blackboard temperature of 63±3°C without water spray.

The exposed samples were periodically subjected to tensile tests, and the time required for each sample to reduce its elongation to its initial value of 50 inches was defined as the deterioration time.

Also, from the above 0.5 thickness sheet, 50 x 50 r
A test piece of RA was prepared, and the change in transparency over time at room temperature was measured according to JIS K-7105 by haze measurement and
Observe the changes in the sheet surface with the naked eye and check the blue table 1 Weight width**] Haze: Difference from initial value ([(-Ha,)[,7
IEI K-7105] Prison lead 5 No ni bloom 4: Slight plume 3 ni bloom 2: Violent plume 1; Very violent plume

Claims (1)

[Scope of Claims] A stabilizer for synthetic polymers, comprising as active ingredients at least one piperidine compound having the following general formulas (Ia) to (Id) and at least one organic carboxylic acid. ▲ 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) ▲ Mathematical formulas, chemical formulas, tables, etc. ▼ (I d) In the above formula, R^1 represents a hydrogen atom, methyl group, benzyl group, acetyl group, or a group having the formula ▲ Numerical formula, chemical formula, table, etc. ▼, and n is 1 to 4 When n is 1, R^2 is a group having the formula -COR^5 [wherein R^5 is an alkyl group having 1 to 17 carbon atoms, or an alkyl group having 2 to 4 carbon atoms] An alkenyl group, a phenyl group, a group having the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or a group having the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (wherein R^1 is the same as above) Show the significance, R^
6 represents an alkyl group having 1 to 8 carbon atoms. ) is shown. ], when n is 2, R^2 is a group having the formula -CO-R^7-CO- (wherein R^7 is an alkylene group having 1 to 20 carbon atoms, a carbon number Indicates a cycloalkylene group having 5 to 7 members, a phenylene group, a group having the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or a group having the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼), one The acyl group has the formula -OR^3
An aliphatic or aromatic triacyl group or two acyl groups forming an ester bond with a group having the formula -OR (wherein R^3 has the same meaning as described below)
It represents an aliphatic or aromatic tetraacyl group forming an ester bond with a group having ^3 (in the formula, R^3 has the same meaning as described below), and when n is 3, R^ 2 is an aliphatic or aromatic triacyl group or a group in which one acyl group has the formula -OR^3 (
In the formula, R^3 has the same meaning as described below. ) represents an aliphatic or aromatic tetraacyl group forming an ester bond with n is 4, R^2 represents an aliphatic or aromatic tetraacyl group, and R^3 has 1 to 18 carbon atoms. R^ represents a group having the formula ▲There are numerical formulas, chemical formulas, tables, etc.▼ (in the formula, R^1 and R^3 have the same meanings as those described above). show.