JPS6049658B2 - Stabilizer for polymer materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stabilizer for synthetic polymer materials containing a novel hydantoin derivative and its acid addition salt as an active ingredient.

Certain hydantoin derivatives are used as stabilizers for synthetic polymeric materials, e.g., US Pat. No. 3,542,729, CHOCH2
Indicates a group having CHCH2-1 ±1.

Z indicates the same meaning as described above.

R2 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an allyl group or a benzyl group.

X is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, 3 or 4
alkenyl radicals having up to 18 carbon atoms, cyanoalkyl radicals having 2 or 3 carbon atoms, 2●3-epoxypropyl radicals, benzyl radicals, aliphatic acyl radicals having up to 18 carbon atoms, or of the formula -CH2CH or a group having -CH2COOR6.

R3 represents an alkyl group having 1 to 4 carbon atoms.

R4 represents a hydrogen atom, a methyl group or a phenyl group.

R5 is a hydrogen atom, an alkyl group, allyl group, benzyl group having 1 to 8 carbon atoms, or an aliphatic, aromatic, araliphatic or alicyclic acyl group having 18 or more carbon atoms (the acyl The aromatic moiety may be optionally substituted with an alkyl group and/or a hydroxy group having 1 to 4 carbon atoms.

R6 represents an alkyl group having 1 to 18 carbon atoms, and an alkenyl group having 3 or 4 carbon atoms represents a phenyl group.

1 indicates 2 or 3.

Y is when I is 2, formula 1n or Indicates a group having

m and n represent integers from 1 to 10.

R7 represents a hydrogen atom or a methyl group.

W is the formula or Indicates a group having

The hydrogen atom in R8 represents a halogen atom.

p represents 1 or 2.

q represents an integer from 1 to 10.

Z is a hydrogen atom, an alkyl group, an allyl group, a benzyl group having 1 to 18 carbon atoms, an aliphatic, aromatic, araliphatic or cycloaliphatic acyl group having 18 or less carbon atoms (the acyl The aromatic moiety of optionally contains an alkyl group having 1 to 4 carbon atoms and/or
or hydroxy group may be substituted), or a group having the formula -P(0R12)2.

R9 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

RlOl represents an alkyl group having 18 carbon atoms, a phenyl group (the phenyl may be optionally substituted with a methyl group, a chlorine atom or a bromine atom), a naphthyl group or a cyclohexyl group.

Rll represents an alkyl group in which the hydrogen atom has 1 to 4 carbon atoms.

Rl.

represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a group having the formula.

Rl3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Y is 1 is 3, Ceremonial items.

[,,N saw,. 6z again (oshi Hυshi 12shi Hshi FI2
--1. I. Indicates a group having 7.

Z indicates the same meaning as described above.

In formula 1, when R2 is an alkyl group having 1 to 18 carbon atoms, it is, for example, methyl, ethyl, n-propyl,
It can be n-butyl, octyl, dodecyl or octadecyl, preferably an alkyl group having 1 to 8 carbon atoms, most preferably a methyl group.

When X is an alkyl group having 1 to 18 carbon atoms, it is, for example, methyl, ethyl, n-propyl, n-
-butyl, octyl, dodecyl or octadecyl, preferably an alkyl group of 1 to 4 carbon atoms, most preferably a methyl group.

If X is an alkenyl group having 3 or 4 carbon atoms, it can be for example allyl or 2-butenyl;
Allyl is preferred.

If x is a cyanoalkyl group having 2 or 3 carbon atoms, it can be, for example, cyanomethyl or 2-cyanoethyl.

If X is an aliphatic acyl group having up to 18 carbon atoms, it can be, for example, a formyl, acetyl, propionyl, butyryl, octanoyl, lauroyl, palmitoyl or stearoyl group or an alkenoyl group such as acryloyl or crotonoyl.

Preferred are alkanoyl groups having 2 to 4 carbon atoms and alkenoyl groups having 3 or 4 carbon atoms, most preferably acetyl. X is the formula -COCH2
When it is a group having CH2----/゛ni0H,
R3 can be an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl or tert-butyl, preferably tert-butyl, and such groups include, for example, 3-(
3-methyl-5-tert-butyl-4-hydroxyphenyl)propionyl or 3-(3,5-di-tert-butyl-4-
hydroxyphenyl)propionyl.

/ When X is a group having the formula --CH2CH8, R4 is a hydrogen atom, a methyl group or a phenyl group, preferably a hydrogen atom, and R5 is a hydrogen atom; having 1 to 8 carbon atoms Alkyl groups, such as methyl, ethyl, n
Butyl or octyl, preferably an alkyl group having 1 to 4 carbon atoms; an allyl group: a benzyl group; or an aliphatic, aromatic, araliphatic or cycloaliphatic acyl group having up to 18 carbon atoms (The aromatic moiety of the acyl may be optionally substituted with an alkyl group and/or a hydroxy group having 1 to 4 carbon atoms), preferably of the formula -CORl
4 (wherein Rl4 is an alkyl group having 1 to 17 carbon atoms; an alkenyl group having 2 or 3 carbon atoms; it may be optionally substituted with up to 3 substituents, and the substituents are A phenyl group which is the same or different C1-4 alkyl or hydroxy; a benzyl group; a 3●5-di-tert-butyl-4-hydroxyphenethyl group; a styryl group; or a cyclohexyl group);
For example, acetyl, propionyl, valeryl, octanoyl, 2-ethylhexanoyl, lauroyl, palmitoyl, stearoyl, acryloyl, crotonoyl, methacryloyl, benzoyl, o-, m- or p-toluoyl, p-tert-butylbenzoyl, salicyloyl, 3
- May be 5-di-tert-butyl-4-hydroxybenzoyl, phenylacetyl, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl, cinnamoyl, cyclohexanecarbonyl.

Optimally -CH2CH" is a group having the formula -CH2CH2OR5, where R5 is a hydrogen atom, an alkanoyl group having from 2 to 18 carbon atoms or a benzoyl group; when X is a group having the formula -CH2COOR6 , R6 is an alkyl group having 1 to 18 carbon atoms,
For example, methyl, ethyl, n-butyl, octyl, dodecyl, preferably an alkyl group having 1 to 4 carbon atoms; an alkenyl group having 3 or 4 carbon atoms, such as allyl or 2-butenyl; or a phenyl group It can be.

In the case of 1=2, when Y is a group having the formula, m is an integer from 1 to 10, preferably 1, and R7 is a hydrogen atom or a methyl group, preferably a hydrogen atom.

When Y is a group having the formula, n is an integer from 1 to 10, preferably from 1 to 3, especially 1.

And W is the formula 4-■1? 4? In the case of a group having V, R8 can be a hydrogen atom or a halogen atom such as chlorine, bromine, R8 is preferably a hydrogen atom,
p is 1 or 2.

Examples of such groups include alkanoyl groups and benzoyl groups.

In particular, -CORl5 of z is preferably the same group as the aliphatic acyl group of X or one CORl4 of R5. When z has the formula 1°C0N8, R9 can be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl or n-butyl, and RlO has 1 to 18 carbon atoms. alkyl groups, such as methyl, ethyl, n-butyl, octyl or octadecyl; phenyl groups (which may be substituted with methyl, chlorine or bromine), such as phenyl, o-, m- or It can be p-tolyl, 0-, m- or p-chlorophenyl or o-, m- or p-bromphenyl; an α- or β-naphthyl group; or a cyclohexyl group.

Suitable 1℃0N? is a group having the formula -CONI(R,O, where RlO is an alkyl group having 1 to 4 or 18 carbon atoms or a phenyl group.

Z is the base -p? In the case of a group having ×, R
ll is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl or n-propyl,
In particular it can be methyl. When Z is a group having the formula -P(0R1.)2, . Rl. is an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl or isopropyl; a phenyl group; or a group (where Rl3 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl or (tert-butyl), and as such a group, for example, Rl6 in the above formula represents a hydrogen atom, a methyl group, an acetyl group, or a group having the formula -CH2CH2ORl8.

Rl7 and Rl8 are the same or different and represent a hydrogen atom, an alkanoyl group having 2 to 18 carbon atoms, or a benzoyl group.

A more preferred compound is the formula (1), in which R16 is a hydrogen atom or a methyl group, and R17 is a hydrogen atom, an alkanoyl group having 2 to 18 carbon atoms, or a benzoyl group.

The hydantoin derivative having formula 1 exists in various stereoisomers when R1 is a methyl group, and such various stereoisomers and mixtures thereof are also included within the scope of the present invention. or -P(0→''))2.

In the above formula 1, R is preferably a hydrogen atom. A compound in which R2 is a hydrogen atom is preferred. Compound L in which X is a hydrogen atom or a methyl group is preferred. Also Y
is preferably a group having the formula (Z is the same as described above).

In the present invention, preferred compounds have the formula (■).

The hydantoin derivatives having formula 1 and acid addition salts thereof of the present invention are produced by any of the following methods, and the reactions themselves are accomplished under known conditions.

(1) In formula 1, R2 and X are hydrogen atoms, and Y
Compound (1) having the formula is produced by reacting compound (2) with epoxy compound (2).

or It also applies to the preparation of the corresponding compounds of formula (1).

The method for producing the raw material compound (■) is based on US Patent No. 23705126.
and disclosed in the specification of JP-A No. 51-139842. The reaction is carried out in the presence or absence of an inert organic solvent by heating a small excess of the calculated amount of Compound (1) and the above epoxy compound, preferably at 50 to 180°C. There are no particular restrictions on the solvent as long as it does not participate in the reaction; for example, ethers such as dioxane, diethylene glycol, and dimethyl ether; dimethylalkylamides such as dimethylformamide and dimethylacetamide; benzene, toluene, xylene, and chlorobenzene. , p-dichlorobenzene; chlorinated or non-chlorinated aromatic hydrocarbons; methanol;
Anhydrous or hydrous alcohols such as ethanol, n- or t-butanol, n-octanol, aqueous methanol, and aqueous ethanol are used, and anhydrous or aqueous alcohols are particularly preferably used. It is also advantageous to carry out the reaction in the presence of basic alkali metal compounds such as sodium hydroxide, potassium hydroxide, potassium carbonate. (2) In formula 1, R2 and X are hydrogen atoms, and Y is the formula 1"゛"-"゜,
It is produced by reacting the alkali metal salt of compound (1) with a halogen compound.

It also applies to the preparation of the corresponding compound ①.

The reaction is advantageously carried out by reacting the alkali metal salt of compound (1) with the above halogen compound in the presence of an inert organic solvent.

For producing the alkali metal salt of compound (1), alkali metal hydroxides or carbonates such as sodium hydroxide, potassium hydroxide, and potassium carbonate are preferably used.

Examples of solvents include dialkylamides such as dimethylformamide and dimethylacetamide; methanol,
Alcohols such as ethanol and n-propanol, or a mixed solvent of these solvents and water are preferably used. The reaction is preferably carried out at room temperature to 150°C. Formula 1
of the compound X. ．． A compound having substituent groups on Z and R2 is produced as follows.

3) In formula 1, a compound in which R2 and Z are hydrogen atoms and x is substituted can be produced by any of the following methods.

(a) In the method of (1) above, in place of compound
is produced by similarly reacting an epoxy compound with a corresponding compound substituted with .

The method for producing the raw material compound of Yanghe is US Patent No. 3,898,303.
and disclosed in the specification of JP-A No. 51-139842. (b) Compound (2) is produced by reacting compound (1) with bisphenol A.

(X'' represents a group similar to X other than a hydrogen atom).

Instead of bisphenol A in the above method, dicarboxylic acid HOCO-+. The corresponding compound (2) can be prepared using CH2'+9.

The method for producing the raw material compound (1) is disclosed in the specification of JP-A-51-139842, which is treated as US Pat. No. 3,941,74. The reaction is carried out in the presence or absence of an inert organic solvent, and the compound ■
and bisphenol A or dicarboxylic acid, preferably by heating to 80 to 180°C.

Examples of solvents include dialkylamides such as dimethylformamide and dimethylacetamide; dioxane,
Ethers such as diethylene glycol diethyl ether; or t-butanol are preferably used.
(c) The compound in which x is a hydrogen atom obtained by the method (1) or (2) above is added to (9), (10) and (
It is produced by method 1 in which substituent X is introduced by method 11).

(4) In the formula 1, a compound in which R2 is a hydrogen atom, X is unsubstituted or substituted, and Z is an alkyl group, allyl group, or benzyl group, (a) in the method of (2) above, the compound In place of (2), the reaction is carried out in the same manner using a corresponding halogen compound in which Z is substituted with the above group, or (b) Z obtained by the above method (1), (2) or (3) is When a compound is a hydrogen atom, an inert organic solvent such as di7
Prepared by reacting a strongly basic alkali metal compound such as sodium hydride or potassium tert-butyrate followed by a halogen compound of the desired group in the presence of methylformamide, toluene, xylene, tetrahydrofuran or dioxane. be done.

The reaction is usually carried out by heating to 50-120'C. (
5) In formula 1, a compound in which R2 is a hydrogen atom, x is unsubstituted or substituted, and z is an acyl group, (a) in the method (2) above, an acyl group is added to Z instead of compound (2). A similar reaction is carried out using a corresponding halogen compound substituted with a group, or (b) a compound obtained by the above method (1), (2) or (3) in which Z is a hydrogen atom or a hydrogen atom. , an activated derivative of a carboxylic acid (acid halide, acid anhydride or acid lower alkyl ester) corresponding to the desired acyl group.
It is produced by reacting.

When using acid esters, the reaction is preferably carried out in an inert organic solvent in the presence of a strong base.

Examples of solvents include benzene, toluene, xylene, n
Aromatic or aliphatic hydrocarbons such as -heptane, n-octane, isooctane are preferably used. Further, as the strong base, for example, a strongly basic alkali metal compound such as sodium methylate, sodium ethylate, potassium hydroxide, or lithium amide, or a titanic acid compound such as tetraisopropyl titanate or tetrabutyl titanate is preferably used. The reaction usually proceeds advantageously by heating to 80-180'C. If acid halides are used, this is advantageously carried out in an inert organic solvent in the presence of an acid binder.

Preferred solvents include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated aliphatic hydrocarbons such as chloroform and trichloroethane; and ethers such as diethyl ether, tetrahydrofuran, and dioxane. .

Preferred examples of acid binders include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; and organic bases such as triethylamine and pyridine. used.

The reaction is usually carried out at 0 to 130°C. When an acid anhydride is used, the reaction is carried out in the presence of an inert organic solvent, or in the absence of an inert organic solvent using an excess of the acid anhydride.
Preferred solvents include aromatic hydrocarbons such as benzene, toluene and xylene; and ethers such as dioxane, tetrahydrofuran and diethylene glycol dimethyl ether.

The reaction is usually carried out at room temperature to 160°C. If R2
When the above R4 ν acylation reaction is carried out using a raw material compound in which Z and Z are hydrogen atoms and X is -℃H2CHOHl, Z and -CH2C
Both R5s of 1 of HOR5 are on the same side.
A compound is produced that is an R4 .group.

Furthermore, if R2, z and x are hydrogen atoms and the acylation reaction is further continued using an excess of acid halide or acid anhydride, then Z and z are the same acyl group. A compound is produced.

(6) In formula 1, a compound in which R2 is a hydrogen atom, X is unsubstituted or substituted, and Z is -CON(R9)(RlO) is a compound in which (a) Z is a hydrogen atom. Carbamic acid halide C1-CON (R9) (RlO)
It is produced by reacting.

The reaction is advantageously carried out in an inert organic solvent in the presence of an acid binder.

As the solvent, for example, ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene and toluene are preferably used. In addition, examples of acid binders include triethylamine, N·N-diethylaniline,
Organic bases such as pyridine are preferably used. The reaction is usually carried out at -10 to 1200C. (b) If
When the group to be introduced is -CONHRlO, the isocyanate RlONC is added to the corresponding compound where Z is a hydrogen atom.
It can also be produced by reacting O. The reaction is carried out in the presence or absence of an inert organic solvent.

As the solvent, aromatic hydrocarbons such as benzene, toluene, and xylene; and ethers such as tetrahydrofuran and dioxane are preferably used. The reaction is usually carried out at 50-130°C. (7) In equation 1,
A compound in which R2 is a hydrogen atom, X is unsubstituted or substituted, and Z is or -P(0R12)2 is produced by subjecting the corresponding compound in which Z is a hydrogen atom to a phosphorus halide reaction. .

The reaction is advantageously carried out in an inert organic solvent in the presence of a base.

Examples of solvents include dioxane, tetrahydrofuran,
Ethers such as diethyl ether; aliphatic, alicyclic or aromatic hydrocarbons such as n-hexane, cyclohexane, benzene and toluene; dialkylamides such as dimethylformamide and dimethylacetamide are preferably used. Ru. As the base, tertiary amines such as triethylamine and N●N-diethylaniline are preferably used. The reaction is usually carried out at -10 to 80°C. (8) In formula 1, the compound in which X and/or Z are unsubstituted or substituted and R2 is an alkyl group, allyl group or benzyl group is (a) produced by the method of (1) to (7) above. A halogen compound R is added to the corresponding compound in which R2 is a hydrogen atom in the presence of an alkali metal compound.
It is produced by reacting 2Cl.

In carrying out the above reaction, X is
or when Z is a hydrogen atom, this can be advantageously achieved by protecting these hydroxyl groups in advance, if necessary.

Such protection may be carried out by methods commonly used for protecting hydroxyl groups, such as, for example, tetrahydropyranyl etherification or p-nitrobenzoylation. The reaction is JP-A-49-7
2332, and is usually advantageously carried out in an inert organic solvent.

Ethers such as tetrahydrofuran and dioxane; amides such as dimethylformamide and hexamethylphosphoric triamide; aromatic hydrocarbons such as benzene and toluene are preferably used as the solvent, and as the alkali metal compound, Sodium hydride, butyl lithium, sodium amide, potassium carbonate and the like are preferably used. The reaction is usually carried out at room temperature to 160°C. (b) Compounds in which R2 is a lower alkyl group, particularly methyl or ethyl, can also be produced by reacting a corresponding compound in which R2 is a hydrogen atom with di-lower alkyl sulfate (R2)2S04.

Furthermore, when a raw material compound in which not only R2 but also Z and/or X are hydrogen atoms is used, a compound in which R2, Z and/or X are substituted with the same lower alkyl group is produced.
The reaction is carried out in the presence or absence of an inert organic solvent.

As the solvent, for example, ethers such as dioxane and tetrahydrofuran; lower aliphatic ketones such as acetone; and aromatic hydrocarbons such as benzene and xylene are preferably used. Furthermore, the reaction can be carried out using, for example, sodium hydroxide,
It is suitably carried out in the presence of an alkali metal hydroxide such as potassium hydroxide; an alkali metal carbonate such as potassium carbonate. The reaction is usually carried out at room temperature to 150°C. (9) In formula 1, R2 and Z are unsubstituted or substituted,
A compound in which X is a methyl group can also be produced by reacting a corresponding compound in which X is a hydrogen atom with formic acid and formaldehyde by a Leukartower-Ratzha reaction.

(10) In formula 1, a compound in which R2 and Z are unsubstituted or substituted and X is 1"21'"1" is a compound in which It is produced by reacting alkylene oxides such as

The reaction is preferably carried out using an alcohol such as methanol, ethanol or propanol as a solvent in the presence of an acidic catalyst such as sulfuric acid or hydrochloric acid.

The reaction is usually carried out at 60-1600C. The hydroxy compound thus obtained can be converted into a desired ester compound or ether compound by further acylation or alkylation. (11) In formula 1, R2 and Z are unsubstituted or substituted, and X is an alkyl group, an alkenyl group, a cyanoalkyl group, a 2●3-epoxypropyl group, a benzyl group, a L. Compounds having the group 1''゜T゛1--゛ or -CH.COOR6 are prepared by reacting the halogen compound X-Cl with the corresponding compound in which X is a hydrogen atom.

The reaction is carried out in the presence or absence of an inert organic solvent according to the method described in US Pat. No. 3,941,744. Examples of solvents include aromatic hydrocarbons such as benzene, toluene, and xylene; chlorinated hydrocarbons such as chloroform, trichloroethane, and chlorobenzene;
Amides such as dimethylformamide, dimethylacetamide and hexamethylphosphoric triamide are preferably used. The reaction is usually carried out at room temperature to 180°C. (12) In formula 1, R2 is unsubstituted or substituted, and Z
is substituted, and X is an aliphatic acyl group or
A compound in which

The reaction is carried out by the method described in (5) above.

(13) The acid addition salt of the compound of formula (1) is prepared by neutralizing the compound of formula (1) with a suitable acid.

It is preferably carried out in an inert organic solvent or a mixed solvent with water. The hydantoin derivatives of formula 1 and acid addition salts thereof of the present invention have low thermal sublimation properties and are effective in stabilizing a wide range of synthetic polymers against photo and thermal degradation. Synthetic polymers stabilized by this method include: Olefin and diene polymers Homopolymers of olefins and dienes (e.g. low density, high density and crosslinked polyethylene, polypropylene, polyisobutylene, polymethylbutene-1, polymethylpentene-1, polyisoprene and polybutadiene), such homopolymers (e.g. mixtures of polypropylene and polyethylene, polypropylene and polybutene-1, or polypropylene and polyisobutylene), and copolymers of olefins and dienes (e.g. ethylene-propylene copolymer, propylene-butene-1 copolymer, propylene-isobutene copolymer, ethylene -butene-1 copolymers and terpolymers of ethylene and propylene with dienes such as hexadiene, dicyclopentadiene or ethylidene norbonolenene) styrene polymers polystyrene, styrene or α-
Copolymers of methylstyrene (e.g., styrene-butadiene copolymers, styrene-acrylonitrile copolymers, styrene-acrylonitrile-methyl methacrylate copolymers, styrene-acrylonitrile-acrylic ester copolymers, styrene modified with acrylic ester polymers to provide impact strength) - an acrylonitrile copolymer and a styrene polymer modified with EPDM to provide impact strength),
and graft copolymers of styrene (e.g., graft polymers of styrene on polybutadiene, graft polymers of styrene and acrylonitrile on polybutadiene, commonly referred to as acrylonitrile-butadiene-styrene or ABS plastics, and mixtures thereof with the above-mentioned styrene copolymers), vinyl halides, and vinylidene. Polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene, chlorinated rubber, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinyl acetate copolymer, vinylidene chloride-vinyl acetate copolymer; polymer of α/β monounsaturated acids and their derivatives Polyacrylic esters and polymethacrylic esters, polyacrylamides and polyacrylonitrile; polymers of unsaturated alcohols and unsaturated amines or their acyl derivatives or acetals polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polymaleic acid Vinyl, polyvinyl butyral, polyallyl phthalate, polymelamine allyl and the monomers mentioned above. Copolymers of polymers and other types of vinyl compounds (
(e.g. ethylene-vinyl acetate copolymers) epoxy polymers Homopolymers and copolymers of epoxy compounds (e.g. polyethylene oxide) and polymers of bisglycidyl ether compounds; polyacetals, polyalkylene oxides and polyphenylene oxides polyoxymethylene, oxymethylene-ethylene oxide copolymers, polyoxyethylene , polypropylene oxide, polyisobutylene oxide and polyphenylene oxide; polyurethanes and polyurea polycarbonates 11υ polysulfone polyamides and copolymers polyamides derived from diamines and aliphatic or aromatic dicarboxylic acids and/or aminocarboxylic acids derived from the corresponding lactams and copolyamides such as nylon-6, nylon-6/6, nylon-6/
101 Nylon-11, Nylon 12; polyesters derived from dicarboxylic acids and dialcohols and/or from oxyacids or their corresponding lactones, such as polyethylene glycol terephthalate, poly 1,4-dimethylol-cyclohexane terephthalate Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas or melamine on the other hand, such as phenol-formaldehyde resins, urea-formaldehyde resins and melamine-formaldehyde resins; alkyd resins, such as glycero-luthalic acid. resins and mixtures thereof with melamine-formaldehyde resins; unsaturated polyester resins; unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols and obtained using vinyl compounds as crosslinking agents; and those modified by chlorinating it to make it flame retardant.

The amount of stabilizer of the present invention required for effective stabilization of the polymer is:
It depends on various factors, such as the type and nature of the polymer in question, its intended use, and the presence of other stabilizers.

Typically, the stabilizer of the present invention is added at 0.00% based on the weight of the polymer.
0.01 to 5% by weight is sufficient, but the most effective range varies depending on the type of polymer: 0.01 to 2% for olefin, diene, and styrene polymers.
．． 0% by weight, preferably 0.02 to 1. Nominal weight %; 0.0 for vinyl chloride and vinylidene chloride polymers
1 to 1. % by weight, preferably from 0.02 to 0.5% by weight; and for polyurethane and polyamide 0
．． 01 to 5. Call volume %, preferably 0.02 to 2. Call volume%. If desired, two or more of the stabilizers of the present invention can be used together. The stabilizers of the present invention are readily incorporated into the polymer by conventional techniques at any convenient stage prior to manufacturing the shaped article. for example,
The stabilizer can be mixed with the polymer in dry powder form, or a suspension or emulsion of the stabilizer can be mixed with a solution, suspension or emulsion of the polymer. The stabilized polymeric compositions of the present invention may also optionally contain various additives conventional in the field of polymer technology, such additives as described in British Patent Specification 1401924, pages 11-13. It is described in.

The invention is further illustrated in the following examples, in which all parts and percentages are by weight.
Example 1 2.2-bis(4-[2-hydroxy-3-(7.7.
8,9,9-pentamethyl-2,4-dioxo 1,3
・8-triazaspiro[4,5]dec-3-yl)propoxy]phenyl)pC]/Man (Example Compound 2) 7.7◆8.9●9-Pentamethyl-1.3.8-triazaspiro[ 4.5] Deccan-2.
4-dione 26.3y12・2-bis[p-(2●3-
17.0 y of epoxypropoxy)phenyl]propane and 0.5 da of potassium hydroxide were added, and the mixture was heated under reflux for 8 hours with stirring.

After the reaction was completed, the reaction mixture was cooled, the precipitated crystals were washed with methanol, and then recrystallized from benzene to obtain the desired compound as white crystals having a melting point of 241-244°C. Example 2 2.2-bis(4-[2-hydroxy-3-(7.7.
9,9-tetramethyl-2,4-dioxo 1,3,8
-triazaspiro[4,5]-dec-3-yl)propoxy]phenyl)propane (Exemplary Compound 1) 7,7,9,9-tetramethyl-1,3,8-toazaspiro[4,5] in 50% ethanol 400T11 Deccan-2/4
-dione 24.0y1 potassium hydroxide 0.5y and 2.2
-Bis[4-(2,3-epoxypropoxy)phenyl]propane (17.0y) was reacted according to the method of Example 1 to obtain the desired compound as crystals having a melting point of 117-119°C.

Example 3 2,2-bis(4-[2-hydroxy-3-(7,9-
Diethyl-6,7,9-trimethyl-2,4-dioxo1,3,8-triazadispiro[4,5]decy3-
yl)propoxy]phenyl)propane (Exemplary Compound 1
04) 7,9-diethyl-6,7,9 in a mixture of 150 ml of dimethylformamide and 20 ml of methanol
-Trimethyl-138-triazaspiro[4,5]decane-2,4-dione 4.1q1 Potassium hydroxide 0.05
When 2.5 q of 9 and 2-bis[4-(2,3-epoxypropoxy)phenyl]propane were reacted according to the method of Example 1, the desired compound was obtained as a white powder.

This product has an Rf value of 0.66 by thin layer chromatography using silica gel [developing solvent = mixed solvent of ethyl acetate, nibenzene, ethanol, and nitriethylamine (8:111)].
showed that. Example 4 1.1″-[isopropylidene bis(p-phenyleneoxy)]bis[3-[p-(p-[2-hydroxy-3
-(7, 7, 8, 9, 9-pentamethyl-2 ● 4-dioxo 1 ● 3, 8-triazaspiro [4.5] Deci 3
-yl)propoxy]-α・α-dimethylbenzyl)phenoxy]-2-propanol] (Exemplary Compound 108)
250 mt of methanol and 50 mt of dimethylformamide
7,7,8,9,9-pentamethyl-1,3◆8-triazaspiro[4,5]de"can-2,
4-dione 16.0y1 potassium hydroxide 0.2y and 1
・1″-[isopropylidene bis(p-phenyleneoxy)]bis[3-(p-[p-(2,3-epoxypropoxy)-α・α-dimethylbenzyl]phenoxy)-
2-Propano. When 25.0y was reacted according to the method of Example 1, the desired compound was obtained as a white powder.

This product showed an Rf value of 0.42 in thin layer chromatography using silica gel (developing solvent = mixed solvent of ethyl acetate nibenzene ethanol nitriethylamine (20:2:2:1)). Example 5 2.2-bis(4-[2-hydroxy-3-(7.7.
9,9-tetramethyl-2,4-dioxo 1,3,8
-Triaza<spiro[4,5]dec-3-yl)propoxy]cyclohexyl)propane (Exemplary Compound 118)
7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane-2 in 300 ml of methanol
・When 40.0y of 4-dione, 2.0f of potassium hydroxide and 17.5y of 2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane are reacted according to the method of Example 1, a white The desired compound was obtained as a powder.

This product has an Rf value of 0.5 in thin layer chromatography using silica gel [developing solvent = mixed solvent of ethyl acetate nibenzene ethanol nitriethylamine (8:1:11)].
6 was shown. Example 6 Bis[2-hydroxy-3-(7,7,8,9,9-pentamethyl-2,4-dioxo1,3,8-triazaspiro[4,5]dec-3-yl)propyl]adipate (exemplified compound 126) 7 in 80ml t-butanol
・7,8,9,9-pentamedyl-13,8-triazaspiro[4,5]decane-2,4-dione 9.6y1 potassium hydroxide 0.1y and bis(2,3-epoxypropyl)adipate 5.2q When the reaction was carried out according to the method of Example 1, the desired compound was obtained as white crystals having a melting point of 180-184°C.

Example 7 Bis[2-hydroxy-3-(7,7◆8,9,9-pentamethyl-2,4-dioxo1,3,8-triazaspiro[4,5]dec.3-yl)propyl]phthalate (example) Compound 130) Dimethylformamide 200
7, 7, 8, 9, 9-pentamethyl-1 in TrL1.
3,8-triazaspiro[4,5]decane-2,4-dione 24.0y1 potassium hydroxide 0.5 da and bis(2
- 12.09 of 3-epoxypropyl) phthalate was reacted according to the method of Example 1 to obtain the desired compound as a white powder.

This product has an Rf value of 0 in thin layer chromatography using silica gel [developing solvent] mixed solvent of ethyl acetate, diethanol, nitriethylamine (8:1:1:1)]
．． It showed 47. Example 8 Bis[2-hydroxy-3-
(7,7,8,9,9-pentamethyl-2,4-dioxo1,3,8-triazaspiro[4,5]decy3-
yl)propyl]-1,2-cyclohexanedicarboxylate (Exemplary Compound 147) 7,7,8,9,9-pentamethyl-1●3,8-triazaspiro[4,5]decane-2,4- in 300 ml of methanol Zeon 27.
When 0 da, 0.2 y of potassium hydroxide and 14.0 y of bis(2,3-epoxypropyl) 1,2-cyclohexanedicarboxylate are reacted according to the method of Example 1, it has a melting point of 119-127 C. The desired compound was obtained as white crystals.

Example 9 Ethylene glycol bis[2-hydroxy-3-(7
・7,8,9,9-pentamethyl-2,4-dioxo 1●3,8-triazaspiro[4●5]dec-3-yl)propyl]ether (exemplified compound 166) 7.7.8 in methanol 60ml 9.9-pentamethyl-1◆
10.0y of 3,8-triazaspiro[4,5]decane-2,4-dione, 0.1y of potassium hydroxide, and 3.0y of ethylene glycol bis(2,3-epoxypropyl) ether according to the method of Example 1. Upon reaction, the desired compound was obtained as white crystals with a melting point of 213-215°C.

Example 10 Nonaethylene glycol bis[2-hydroxy-3-
(7◆7.8.9.9-pentamethyl-2.4-dioxo1.3.8-triazaspiro[4.5]decy3-
yl)propyl]ether (Exemplary Compound 169) 7,7,8,9,9-pentamethyl-1,3,8-toazaspiro[4,5]decane-2,4 in 100 ml of methanol
- When 5.8 g of dione, 0.1 y of potassium hydroxide, and 5.3 y of nonane ethylene glycol bis(2,3-epoxypropyl) ether are reacted according to the method of Example 1, the desired colorless viscous oil is obtained. The compound was obtained.

This product can be used for thin layer chromatography using silica gel [developing solvent = ethyl acetate ni methanol nitriethylamine (
2:1:0.03) mixed solvent] showed an Rf value of 0.38. Example 11 Glycerol tris[2-hydroxy-3-(7.7
・8,9,9-pentamethyl-2,4-dioxo 1・
3●8-triazaspiro[4,5]dec-3-yl)propyl]ether (exemplified compound 177) methanol 80
7, 7, 8, 9, 9-pentamethyl-1, 3, in mt
8-Triazadispiro[4,5]decane-2,4-dione 12.0 V1 Potassium hydroxide 1.1 and glycerol Tris(2,3-epoxypropyl) ether 4.
When 1y was reacted according to the method of Example 1, the desired compound was obtained as a white powder.

This compound showed an Rf value of 0.45 by thin layer chromatography using silica gel [developing solvent = mixed solvent of benzene diacetate, ethyl dichloroform, nimethanol, and nitriethylamine (4:4:4:1:1)]. Example 12 Tris[2-hydroxy-3-(7.7.8.9.9-
Pentamethyl-2,4-dioxo 1,3,8-triazaspiro[4,5]dicy,3-yl)propyl]isocyanurate (Exemplary Compound 174) Methanol 200
7,7,8◆9,9-pentamethyl-1,3, in mt
8-triazaspiro[4.5]decane-2.4-dione 40.0q1 potassium hydroxide 1.0y and tris(2.
When 0.0 da of 3-epoxypropyl isocyanurate was reacted according to the method of Example 1, the melting point was 155-15.
The desired compound was obtained as white crystals with TC.

Example 13 2,2-bis(4-[2-capryloyloxy-3-(
7,7,8,9,9-pentamethyl-2,4-dioxo1,3,8-triazaspiro[4,5]dec-3-yl)propoxy]phenyl)propane (Example Compound 37)
) 2,2-bis(4-[2-hydroxy-3-(7,7,8,9,9-pentamethyl-2,
4-dioxo 1,3,8-triazaspiro [4,5]
Dec-3-yl)propoxy]phenylpropane 8.0
A mixture of 15.0y of V and n-caprylic anhydride was heated under stirring at 140-150<0>C for 3 hours.

Next, 10.0 y of potassium carbonate was added little by little to this mixture, and the mixture was further heated at the same temperature for 2 hours with stirring. After the reaction was completed, the reaction mixture was cooled and 200 mt of benzene was added.
The benzene solution was then washed with a 3% aqueous potassium carbonate solution and dried over anhydrous potassium carbonate. The solvent was distilled off from the reaction mixture, and the resulting residue was diluted with petroleum benzyl-benzene (2
:1) When recrystallized from a mixed solvent, the melting point is 131-135.
The desired compound was obtained as white crystals with . Example 14 2.2-bis(4-[2-acetoxy 3-(7.7.
8,9,9-pentamethyl-2,4-dioxo 13.
8-Triazadispiro[4,5]dec-3-yl)propoxy]phenyl)propane (Exemplary Compound 35) 2,2-bis(4-[2-hydroxy-3) obtained in Example 1
-(7,7,8,9,9-pentamethyl-2,4-dioxo1,3,8-triazaspiro[4,5]decy3
A mixture of 4.0y -yl)propoxy]phenyl)propane and 1007TL1 acetic anhydride was heated at 120-130°C for 6 hours.

The reaction product was then treated according to the method of Example 13 to yield the desired compound as white crystals with a melting point of 229-23rC. Example 15 2,2-bis(4-[2-benzoyloxy-3-(7
・7,8,9,9-pentamethyl-2,4-dioxo1,3,8-triaza[4,5]dec-3-yl)propoxy]phenyl)propane (Example Compound 45)
) 2,2-bis(4-[2-l-hydroxy-3-(7,7,8,9,9-pentamethyl-2) obtained in Example 1
●4-dioxo1,3,8-triazaspiro [4,5
[Dec-3-yl)propoxy]phenyl)propane 4
．． 0y1 potassium carbonate 4.0y and benzoic anhydride 4.0y
When q is reacted according to the method of Example 13, the melting point is 20
The desired compound was obtained as white crystals with a temperature of 6-211°C.

Example 16 2,2-bis(4-[2-dodecyloxy-3-(7,
7,8,9,9-pentamethyl-2,4-dioxo 1
◆3●8-Triazaspiro [4.5] Deci3-yl)
Propoxy]phenyl)propane (Exemplary Compound 34) 2,2-bis(4-[2-hydroxy-3-(7,7,8,9,9-pentathyl-2,4-dioxo 1. 3.8-Triazaspiro [4.5] Deci 3
1.5y of sodium hydride was added to a solution of 8.2y of -yl)propoxy]phenyl)propane dissolved in 150ml of dimethylformamide under stirring, and the mixture was heated at 50-60°C for 2 hours.
Stir for hours.

Next, 10.0 y of n-dodecyl bromide was added dropwise, and the mixture was further heated and stirred at 50-60°C for 2 hours and then at 70-80°C for 4 hours. After the reaction was completed, the reaction mixture was concentrated under reduced pressure, and then 200 ml of benzene was added to the resulting residue, and the benzene solution was washed successively with a 2% aqueous sodium carbonate solution and water. After drying the reaction mixture over anhydrous sodium carbonate, the solvent was distilled off from the reaction mixture, and the resulting residue was subjected to column chromatography on silica gel [eluent = ethyl acetate nibenzene niethanol nitriethylamine (
32:4:5:1) mixed solvent]
The desired compound was obtained as a colorless viscous oil. This product has an Rf value of 0.5 by thin layer chromatography using silica gel [developing solvent = mixed solvent of ethyl acetate nibenzene ethanol nitriethylamine (20:2:2:1)]
3 was shown. Example 17 2,2-bis(4-[2-methoxy3-(1,7,7
・8,9,9-hexamethyl-2,4-dioxo 1・
3,8-triazaspiro[4,5]dec-3-yl)propoxy]phenyl)propane (Exemplary Compound 92) 2,2-bis(4-[2-hydroxy-3-(7,7) obtained in Example 1・8,9,9-pentamethyl-2,4-dioxo1,3,8-tria5zaspiro[4,5]dec-3-yl)propoxy]phenyl)propane 2.0q
and 1.5y of sodium hydroxide in 100ml of dioxane
In addition to this, 3.5y of dimethyl was added dropwise while stirring and heating at 40 to 50°C.

After the dropwise addition was completed, the mixture was further heated and stirred at 70 to 80°C for 6 hours. After the reaction was completed, the reaction mixture was concentrated under reduced pressure, then benzene was added to the resulting residue, and the benzene solution was added to
% aqueous sodium hydroxide solution and water. The solvent is distilled off, and the resulting residue is purified by column chromatography 4 on silica gel [eluent: mixed solvent of ethyl acetate nibenzene niethanol nitriethylamine (8:1°1:1)] to obtain the desired product. The compound was obtained as a white powder. This compound is made of silica gel.
Layer chromatography [Developing solvent = ethyl acetate-benzene-ethanol triethylamine (8:1
:1:1) mixed solvent] showed an Rf value of 0.54.

Example 182.2-bis[4-(2-hydroxy-3-[8-(2-hydroxyethyl)-779.9-tetramethyl-2.4-dioxo1.3.8-triazaspiro[4.5]decy3 −yl]propoxy)phenyl]
Propano (Exemplary Compound 8) 2. obtained in Example 2
2-bis(4-[2-hydroxy-3-(7.7.9.
9-Tetramethyl-2,4-dioxo1,3,8-triazaspiro[4,5]dec-3-yl)propoxy]
phenyl)propane 1.4g, ethylene oxide 3ml
and 1 drop of concentrated hydrochloric acid were added to 60 ml of methanol and heated in a sealed tube at 105-115°C for a specific time.

After the reaction was completed, the reaction mixture was concentrated under reduced pressure, and the resulting residue was purified by successively recrystallizing from benzene and ethanol to obtain the desired compound as white crystals having a melting point of 233-236°C. Example 19 2●2-bis(4-[2-methylcarbamoyloxy-3-(7,7,9,9-tetramethyl-2,4-dioxo1,3,8-triazaspiro[4,5]decy3-
yl)propoxy]phenyl)propane (Exemplary Compound 3
1) 2,2-bis(4-[2-hydroxy-3-(7,7,9,9-tetramethyl-2●4) obtained in Example 2
-Dioxo1,3,8-triazaspiro[4,5]dec-3-yl)propoxy]phenyl)propane 5.0
q and 25.0 q of methyl isocyanate were heated under reflux for 8.5 hours.

After the reaction, excess methyl isocyanate was distilled off from the reaction mixture, and the resulting residue was subjected to column chromatography on silica gel [eluent = ethyl acetate nibenzene nitriethylamine diethanol (24:12:2:1)]
The desired compound was obtained as white crystals having a melting point of 238-242'C. Example 20 2●2-bis(4-[2-phenylcarbamoyloxy-3-(7.7.9●9-tetramethyl-2●4-dioxo1.3●8-triazaspiro[4.5]decy3
-yl)propoxy]phenyl)propane (Exemplary Compound 32) 2,2-bis(4-(2-hydroxy-3-(7.7.9.9-tetramethyl-2.
4-Dioxo 1,3●8-Triazaspiro [4,5]
Dec-3-yl)propoxy]phenyl)propane5.
Example 1
When the reaction is carried out according to method 9, the melting point is 202~20rc.
The desired compound was obtained as a crystal having .

1 Example 212.2-bis(4-[2-acetoxy3-(8-acetyl-7.
7,9,9-tetramethyl-2,4-dioxo 1,3
・8-triazaspiro[4,5]dec-3-yl)propoxy]phenyl)propane (Exemplary Compound 68) 2,2-bis(4-[2-hydroxy-3) obtained in Example 2
-(7,7,9,9-tetramethyl-2,4-dioxo1,3,8-triazaspiro[4,5]dec-3-yl)propoxy]ph,enyl)propane 5q was added to 100 mL of acetic anhydride while stirring. It was heated at 100-110°C for 6 hours.

After the reaction was completed, the reaction mixture was concentrated under reduced pressure, and then 150 TrLt of benzene was added to the resulting residue, and the benzene solution was washed successively with a 2% aqueous sodium carbonate solution and water. The solvent was distilled off from the reaction mixture, and the resulting residue was subjected to column chromatography on silica gel [eluent = ethyl acetate, nibenzene, ethanol, nitriethylamine (
8:1:1:1) to give the desired compound as white crystals with a melting point of 147-149°C. Example 222-Hydroxy-1,3-
Bis(7,7,8,9,9-pentamethyl-2,4-dioxo1,3,8-triazaspiro[4,5]dec-3-yl)propane (Exemplary Compound 164) 7●7●8 in 200mL of dimethylformamide ●9,9-pentamethyl-1,3,8-triazaspiro[4.5]decane-2
- 22.0q of 4-dione and 5.1q of potassium hydroxide were stirred at 50-60°C for 30 minutes.

Next, 9.0 y of 1,3-dibromo-2-propanol was added dropwise L1, and the mixture was further stirred at 100 to 110°C for 6 hours. After the reaction was completed, the reaction mixture was concentrated under reduced pressure, and the resulting residue was washed with a 1% aqueous potassium hydroxide solution, and then recrystallized from a benzene-ethanol (2:1) mixed solvent to give a melting point of 255-256°C. The desired compound was obtained as white crystals. Example 23 Bis[2-hydroxy-3-(
7.7●9.9-tetramethyl-2.4-dioxo 1
・3●8-Triazaspiro [4.5] Deci3-yl)
Propyl]adipate (Exemplary Compound 125) 7・7●9
●9-tetramethyl-1●3,8 triazaspiro [4
・5] Using decane-2,4-dione and bis(2,3-epoxypropyl) adipate as starting materials, a reaction was carried out according to the method of Example 1 to obtain the desired white crystals with a melting point of 132 to 134°C. A compound was obtained.

Example 24 Bis[2-hydroxy-3-(7,7,8,9◆9-pentamethyl-2●4-dioxo1,3,8-triaza[spiro[4,5]dec-3-yl)propyl]terephthalate ( Exemplary compound 144) Performed using 7,7,8,9,9-pentamethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione and bis(2,3-epoxypropyl) terephthalate as starting materials. The reaction was carried out according to the method of Example 1, and the desired compound was obtained as white crystals having a melting point of 139-14rC.

Example 25 Unstabilized polypropylene powder (MF'I-18) 100
part, stearyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate as an antioxidant 0
2 parts and 0.25 part of the stabilizer of the present invention listed in Table 1 were homogenized by kneading one powder at 200° C. in a Brabender Blastograph.

The resulting mass was compression molded into a 2-3 TmIn thick sheet using a laboratory press. This sheet is made using a hydraulic press machine for 26
The film was heated and pressed at 0° C. for 6 minutes at a pressure of 12 tons, and then immediately poured into cold water to obtain a film with a thickness of 0.5 TIrm. By the same method, from 0.5TWL film to 0.
．． A film of 1TmfrL was molded. This film was cut into 50 x 120 TWL test pieces. This test piece is Sunshine Weather Meter blackboard temperature 63±
The exposed samples exposed to light at 3°C were periodically examined to determine the percentage elongation at break for each sample.

The test results are expressed as the ratio of the time taken for the sample to reach 50% of the initial elongation at break and the time taken for the sample to reach 50% of the elongation at break of the control sample without the addition of the stabilizer of the present invention. Shown in 1. Example 26 0.25 parts of the stabilizer of the present invention was added to 1 pounded portion of polystyrene pellets (trade name: Styron 666, manufactured by Asahi Tau Co., Ltd.), and the mixture was kneaded in a Brabender plasticorder at 200°C for 5 minutes. to make it homogeneous.

The homogenized mixture was compression molded at 180°C for 2 minutes.
．． 5? I made it into a thick plate. The obtained plate was exposed to 300 I Terama in a Sunshine Carbon Arc Weathermeter at a blackboard temperature of 563±3 AC. The yellowness (YI3OO) of the exposed plates was measured by the method of AsTrOl925. The results obtained are shown in Table 2. Example 27 Thermoplastic polyurethane (product name: Paraprene Pellet 2)
2S1 Nippon Polyurethane Industries Co., Ltd. product) 100 parts and 1 part of the stabilizer of the present invention were mixed with 3(1) parts of dimethylformamide.
It was uniformly dissolved in all parts.

Claims (1)

[Claims] 1. A stabilizer for synthetic molecular materials consisting of a compound having the formula ▲ mathematical formula, chemical formula, table, etc. ▼ I or an acid addition salt thereof. In the above formula, R_1 represents a hydrogen atom or a methyl group. R_2 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an allyl group, or a benzyl group. X is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, 3 or 4
an alkenyl group with 2 or 3 carbon atoms, a cyanoalkyl group with 2 or 3 carbon atoms, a 2,3-epoxypropyl group, a benzyl group, an aliphatic acyl group with up to 18 carbon atoms, or with the formula ▲mathematical formula There are , chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Or indicates a group having -CH_2COOR_6. R_3 represents an alkyl group having 1 to 4 carbon atoms. R_4 represents a hydrogen atom, a methyl group, or a phenyl group. R_5 is a hydrogen atom, an alkyl group, allyl group, benzyl group having 1 to 8 carbon atoms, or an aliphatic, aromatic, araliphatic or alicyclic acyl group having 18 or less carbon atoms (the acyl The aromatic moiety may be optionally substituted with an alkyl group having 1 to 4 carbon atoms and/or a hydroxy group. R_6 is an alkyl group having 1 to 18 carbon atoms,
It represents an alkenyl group or a phenyl group having 3 or 4 carbon atoms. l represents 2 or 3. When l is 2, Y is the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. Indicates a group with ▼. m and n represent integers from 1 to 10. R_7 represents a hydrogen atom or a methyl group. W is a formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Mathematical formulas, There are chemical formulas, tables, etc. to indicate groups with ▼. R_8 represents a hydrogen atom or a halogen atom. p represents 1 or 2. q represents an integer from 1 to 10. Z is a hydrogen atom, an alkyl group, an allyl group, a benzyl group having 1 to 18 carbon atoms, an aliphatic, aromatic, araliphatic or cycloaliphatic acyl group having 18 or less carbon atoms (the acyl The aromatic moiety of optionally contains an alkyl group having 1 to 4 carbon atoms and/or
or a hydroxy group may be substituted), the formula ▲ has a mathematical formula, chemical formula, table, etc. ▼, ▲ has a mathematical formula, chemical formula, table, etc. ▼ or ▲ has a mathematical formula, chemical formula, table, etc. ▼ . R_9 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R_1_0 represents an alkyl group having 1 to 18 carbon atoms, a phenyl group (the phenyl may be optionally substituted with a methyl group, a chlorine atom or a bromine atom), a naphthyl group or a cyclohexyl group. R_1_1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R_1_2 represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a group having the formula ▲There are numerical formulas, chemical formulas, tables, etc.▼. R_1_3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When l is 3, Y indicates a group having ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. Z indicates the same meaning as described above. 2. A stabilizer for synthetic polymeric materials according to claim 1, which comprises a compound having the formula ▲numerical formula, chemical formula, table, etc.▼II. In the above formula, R_1_6 represents a hydrogen atom, a methyl group, an acetyl group, or a group having the formula -CH_2CH_2OR_1_8. R_1_7 and R_1_8 are the same or different and represent a hydrogen atom, an alkanoyl group having 2 to 18 carbon atoms, or a benzoyl group. 3 In formula II, R_1_6 is a hydrogen atom or a methyl group, and R_1_7
3. The stabilizer for synthetic polymer materials according to claim 2, which comprises a compound in which is a hydrogen atom, an alkanoyl group having 2 to 18 carbon atoms, or a benzoyl group. 4. The stabilizer for synthetic polymer materials according to claim 1, wherein the synthetic polymer materials are olefin and diene polymers.