Stabilizer used in compound having sulfide group, and method for improving stability of compound having sulfide group

Abstract

Provided are: a stabilizer capable of improving the stability of a compound having a sulfide group directly bonded to an aromatic ring or a heterocyclic ring having a molecular weight of 1,000 or less; a composition containing this stabilizer and a compound having the sulfide group; an organic material and / or inorganic material composition containing this composition; and a method for improving the stability of the compound having the sulfide group.　The stabilizer is used for a compound having a sulfide group directly bonded to an aromatic ring or a heterocyclic ring having a molecular weight of 1,000 or less, the stabilizer including at least one stabilizer A selected from phenol-based compounds, aromatic amine-based compounds, sulfur-containing fatty acid-based compounds, phosphite ester-based compounds, phosphine-based compounds, carbamate-based compounds, and benzimidazole-based compounds.

Description

Stabilizer for use in compounds having a sulfide group, and method for improving the stability of compounds having a sulfide group

[0001] The present invention relates to a stabilizer for use in a compound having a sulfide group, and a method for improving the stability of the compound having a sulfide group.

[0002] Resin components are subject to deterioration due to the action of ultraviolet rays, resulting in quality deterioration such as discoloration and a decrease in mechanical strength, which hinders their long-term use. Furthermore, from the viewpoint of reducing health risks such as sunburn and eye tissue damage, and also from the viewpoint of imparting optical functions, various studies have been conducted on blending ultraviolet absorbers into organic and inorganic components to block or absorb ultraviolet rays.

[0003] Conventionally, organic UV absorbers include benzotriazole-based, benzophenone-based, benzoic acid ester-based, and triazine-based UV absorbers. The present inventors have proposed UV absorbers in which a sulfur-containing group having a sulfide group is introduced into such a UV-absorbing skeleton (Patent Documents 1 to 3). This sulfide-containing UV absorber has good compatibility with the matrix resin, can maintain high transparency even when added at high concentrations, has excellent heat resistance, and is characterized by imparting a high refractive index. In particular, UV absorbers such as those with a 2-phenylbenzotriazole skeleton have optical properties that allow them to adequately absorb light in the wavelength range of 250 to 420 nm. Furthermore, they have a high UV absorption effect (molar extinction coefficient), and can efficiently absorb light of this wavelength with the addition of a small amount, thereby efficiently and sufficiently absorbing harmful light in the range of 380 to 420 nm. Furthermore, the slope of the absorption peak in the 350 to 390 nm range is greater than that of conventional UV absorbers, suppressing absorption of light with wavelengths above 420 nm and thereby suppressing initial yellowing of components in which they are incorporated.

[0004] However, ultraviolet absorbers having a sulfide group decompose over time, resulting in a decrease in ultraviolet absorption ability, leaving room for improvement in stability. For example, Patent Document 4 proposes introducing an electron-withdrawing group having a positive Hammett's σp value into triazine to improve the stability of a triazine-based ultraviolet absorber, and using the triazine in combination with an ultraviolet absorber having a maximum absorption wavelength of 340 to 400 nm, but there is little prior art that refers to the technical problem of improving the stability of the ultraviolet absorber itself.

[0005] International Publication No. 2016 / 021664 International Publication No. 2020 / 137819 International Publication No. 2020 / 175474 Japanese Patent Application Laid-Open No. 2011-006517

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a stabilizer capable of improving the stability of a compound having a sulfide group directly bonded to an aromatic ring or heterocycle having a molecular weight of 1,000 or less, a composition containing the stabilizer and the compound having a sulfide group, an organic material and / or inorganic material composition containing the composition, and a method for improving the stability of the compound having a sulfide group.

[0007]

[0009] In order to solve the above problems, the present inventors have conducted extensive research and have found that stability can be improved by combining a compound having a sulfide group directly bonded to an aromatic ring or heterocycle having a molecular weight of 1,000 or less with at least one stabilizer selected from phenolic compounds, aromatic amine compounds, sulfur-containing fatty acid compounds, phosphite ester compounds, phosphine compounds, carbamate compounds, and benzimidazole compounds, and that the stability can be further improved by using a hindered amine compound in combination, thereby completing the present invention.

[0008] That is, the stabilizer of the present invention is a stabilizer used for a compound having a sulfide group directly bonded to an aromatic ring or heterocycle having a molecular weight of 1000 or less, and is characterized in that the stabilizer contains at least one stabilizer A selected from phenolic compounds, aromatic amine compounds, sulfur-containing fatty acid compounds, phosphite ester compounds, phosphine compounds, carbamate compounds, and benzimidazole compounds. The composition of the present invention contains the stabilizer and the compound having a sulfide group. The organic and / or inorganic material composition of the present invention contains the stabilizer, the compound having a sulfide group, and an organic and / or inorganic material. The method of the present invention for improving the stability of a compound having a sulfide group directly bonded to an aromatic ring or heterocycle having a molecular weight of 1000 or less is characterized in that the stabilizer and the compound having a sulfide group are added to an organic and / or inorganic material composition so that they coexist in the composition.

[0009] According to the present invention, the stability of a compound having a sulfide group directly bonded to an aromatic ring or heterocyclic ring and having a molecular weight of 1,000 or less is improved by combining the compound with at least one stabilizer selected from phenolic compounds, aromatic amine compounds, sulfur-containing fatty acid compounds, phosphite ester compounds, phosphine compounds, carbamate compounds, and benzimidazole compounds. Stability is further improved by using a hindered amine compound in combination. Also provided is a composition having improved stability of the sulfide group-containing compound. Also provided is a method for improving the stability of a compound having a sulfide group by adding the sulfide group-containing compound and the stabilizer to an organic material and / or an inorganic material and allowing them to coexist in a composition.

[0010] Hereinafter, embodiments of the present invention will be specifically described. [Substituents, etc.] In the present invention, the "monovalent or divalent group selected from a hydrocarbon group, an unsaturated group, a nitrogen-containing group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, and a halogen atom" includes groups that can adjust heat resistance, refractive index, melting point, stability, light resistance, compatibility with resins, etc., and examples thereof include the following.

[0011] Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alicyclic hydrocarbon group, a combination thereof, etc. Examples of the aliphatic hydrocarbon group include a linear or branched alkyl group, a linear or branched alkenyl group, and a linear or branched alkynyl group.

[0012] Examples of the aromatic hydrocarbon group include groups containing an aromatic ring such as a benzene ring, a naphthalene ring, or an anthracene ring.

[0013] Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and groups containing any of these groups as the skeleton.

[0014] Examples of the unsaturated group include groups containing a carbon-carbon or carbon-heteroatom unsaturated bond, such as a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-oxygen double bond (such as a carbonyl group, an aldehyde group, an ester group, a carboxy group, a carbamate group, a urea group, an amide group, an imide group, a carbamoyl group, or a urethane group), a carbon-nitrogen double bond (such as an isocyanate group), or a carbon-nitrogen triple bond (such as a cyano group or a cyanato group).

[0015] The nitrogen-containing group contains a cyano group, a nitro group, or a primary to tertiary amino group, and preferably has 0 to 10 carbon atoms. The nitrogen-containing group is not particularly limited, but examples thereof include a cyano group, a cyanato group, an isocyanate group, a nitro group, a nitroalkyl group, an amide group, a urea group, a urethane group, an imide group, a carbodiimide group, an azo group, a pyridine group, an imidazole group, a triazine group, an amino group, a primary amino group, a secondary amino group, a tertiary amino group, an aminoalkyl group, a 3,4,5,6-tetrahydrophthalimidylmethyl group, a 2-[6-(2H-benzotriazol-2-yl-)-4-(1,1,3,3-tetramethylbutyl)phenol-yl]-methyl group, and groups containing these.

[0016] The sulfur-containing group includes a thiol group, a thioether group, a sulfide group, a disulfide group, a thioester group, a thioamide group, a sulfonyl group, a sulfo group, a thiocarbonyl group, or a thiourea group, and preferably has 0 to 10 carbon atoms. The sulfur-containing group is not particularly limited, and examples thereof include a thiomethoxy group, a thioethoxy group, a thio-n-propoxy group, a thioisopropoxy group, a thio-n-butoxy group, a thio-t-butoxy group, a thiophenoxy group, a p-methylthiophenoxy group, a p-methoxythiophenoxy group, a thiophene group, a thiazole group, a thiol group, a thioether group, a sulfo group, a sulfide group, a disulfide group, a thioester group, a thioamide group, a sulfonyl group, a thiocarbonyl group, a thiourea group, a thiocarbamate group, a dithiocarbamate group, and groups containing these.

[0017] When the oxygen-containing group contains an aromatic ring group or an alicyclic group, the carbon number is preferably 6 to 12, and when the oxygen-containing group does not contain an aromatic ring group or an alicyclic group, the carbon number is preferably 0 to 18. The oxygen-containing group is not particularly limited, and examples thereof include a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group, a methylphenoxy group, a dimethylphenoxy group, a naphthoxy group, a phenylmethoxy group, a phenylethoxy group, an acetoxy group, an acetyl group, an aldehyde group, a carboxy group, an ether group, a carbonyl group, an ester group, an oxazole group, a morpholine group, a carbamate group, a carbamoyl group, a urea group, an amide group, an imide group, a urethane group, a polyoxyethylene group, and groups containing these.

[0018] The phosphorus-containing group contains a phosphine group, a phosphite group, a phosphonic acid group, a phosphinic acid group, a phosphoric acid group, or a phosphoric acid ester group, and when it contains an aromatic ring group or an alicyclic group, it preferably has 6 to 22 carbon atoms, and when it does not contain an aromatic ring group or an alicyclic group, it preferably has 0 to 6 carbon atoms.

[0019] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0020] <Stabilizer> The stabilizer of the present invention is a stabilizer for improving the stability of a compound having a sulfide group directly bonded to an aromatic ring or heterocyclic ring having a molecular weight of not more than 1000. The stabilizer of the present invention has the effect of suppressing decomposition over time of the compound having a sulfide group and maintaining the effects of the compound having a sulfide group for a long period of time.

[0021] (Stabilizer A) The stabilizer includes at least one stabilizer A selected from a phenol-based compound, an aromatic amine-based compound, a sulfur-containing fatty acid-based compound, a phosphite-based compound, a phosphine-based compound, a carbamate-based compound, and a benzimidazole-based compound.

[0022] The phenolic compound is a compound in which a substituent is bonded to a phenol skeleton, and is not particularly limited. Examples include phenolic compounds in which a methyl group and / or a tert-butyl group is bonded to the phenol skeleton as a substituent. The phenolic compound may have an oxygen-containing group, a nitrogen-containing group, a phosphorus-containing group, or a sulfur-containing group as a substituent, and may have multiple phenol skeletons in one molecule. Among phenolic compounds, those in which an aliphatic hydrocarbon group having 1 to 8 carbon atoms is bonded to one phenol skeleton are preferred, those in which an aliphatic hydrocarbon group having 1 to 6 carbon atoms is more preferred, and those in which an aliphatic hydrocarbon group having 1 to 4 carbon atoms is even more preferred, and among these, those in which a tert-butyl group is bonded are particularly preferred. Among these, compounds having 1 to 4 phenol skeletons, each having two of the aliphatic hydrocarbon groups bonded thereto, are preferred.

[0023] The phenolic compound is not particularly limited, but examples thereof include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyltert-4-hydroxyphenyl)propanamide], 2,6-di-t-butylphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,4,6-tri-t-butylphenol, phenol, 2,6-di-tert-butyl-4-sec-butylphenol, butylhydroxyanisole, tocopherol, 2,6-di-t-butyl-4-hydroxymethylphenol, n-octadecyl-3-(4-hydroxy-3',5'-di-tert-butylphenyl)propionate, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert- Pentyl phenyl acrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, diethyl [(3,5-di-tert-butyl-4-hydroxyphenyl)methyl]phosphonate, 6-tert-butyl-4-[3-[(2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]propyl]-2-methylphenol, 4,6-bis(octylthiomethyl)-o-cresol, propyl gallate, n-octyl gallate, lauryl gallate, 2 , 2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-butylidenebis(6-t-butyl-3-methylphenol), triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, N,N'-bis[2-[2-(3,5-di-tert-butyl-4-tert-hydroxyphenyl)ethylcarbonyloxy)ethyl]oxamide, 4,4'-thiobis(2-tert-butyl-5-methylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, 2,2-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4'-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, N , N'-bis 3-(3',5'di-tert-butyl-4'-hydroxyphenyl)propionylhexamethylenediamine, N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, calcium bis[3,5-di(tert-butyl)-4-hydroxybenzyl(ethoxy)phosphinate], 1,1,3-tris(2-methyl-4-hydroxy-5 -tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-trione, 1,1, 3-tris[2-methyl-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-5-tert-butylphenyl]butane, tetrakis[methylene-3-(3',5',-di-tert-butyl-4-hydroxyphenyl)propionate]methane, ethylene bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyrate], etc. Among these, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl tert-4-hydroxyphenyl)propanamide] is preferred.

[0024] Aromatic amine compounds are compounds in which a nitrogen atom is bonded to an aromatic compound which may have a substituent. Examples of aromatic compounds include aromatic hydrocarbons and heteroaromatic compounds having 1 to 20 carbon atoms. Examples of aromatic hydrocarbons include, but are not limited to, benzene, naphthalene, anthracene, etc. Examples of heteroaromatic compounds include compounds containing a nitrogen atom, an oxygen atom, a sulfur atom, etc. Examples of heteroaromatic compounds include, but are not limited to, triazine, pyrrole, pyrazole, imidazole, pyridine, pyrazine, furan, thiophene, etc.

[0025] The aromatic amine compound is not particularly limited, but examples thereof include 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, N,N'-di-sec-butyl-1,4-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-1,4-phenylenediamine, N-phenyl-1-naphthylamine, 4-isopropylaminodiphenylamine, N,N'-diphenyl-1,4-phenylenediamine, N,N'-di-2-naphthyl-1,4-phenylenediamine, and 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline.

[0026] The sulfur-containing fatty acid compound is a compound in which two aliphatic hydrocarbon groups having 1 to 20 carbon atoms, each of which may have a substituent, are bonded to a sulfur atom, and may contain multiple sulfur atoms in one molecule. The substituent is preferably an ester-containing group, more preferably an alkyl ester group.

[0027] The sulfur-containing fatty acid compound is not particularly limited, but examples thereof include didodecyl 3,3'-thiodipropionate, ditridecyl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythritol tetrakis[3-laurylthiopropionate], stearylthiopropionic acid amide, bis[2-methyl-4-(3-n-alkyl(C12-C14)thiopropionyloxy)-5-t-butylphenyl]sulfide, dioctadecyl disulfide, and 1,1'-thiobis(2-naphthol). Among these, didodecyl 3,3'-thiodipropionate, ditridecyl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, and pentaerythritol tetrakis[3-laurylthiopropionate] are preferred, and didodecyl 3,3'-thiodipropionate and pentaerythritol tetrakis[3-laurylthiopropionate] are more preferred.

[0028] The phosphorous ester (phosphite) compound is not particularly limited, but examples thereof include compounds represented by the following formula (1): 5 ~R 7 and the like, each independently representing a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. The hydrocarbon group is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0029]

[0030] The phosphite ester compound is not particularly limited, but examples thereof include 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, triisodecyl phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tris(mono- and di-nonylphenyl mixed)phosphite, diphenylisooctylphosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl)octylphosphite, diphenylmonodecylphosphite, diphenylmono(tridecyl)phosphite, phenyl-di-isodecylphosphite, diphenylmono(2-ethylhexyl)phosphite, tridecylphosphite, tris(tridecyl)phosphite, trilauryltrithiophosphite, diphenylisooctyl ... Examples of suitable phosphate groups include stearyl pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra(tridecyl)pentaerythritol tetraphosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, tetrakis(2,4-di-t-butyl-5-methylphenyl)-4,4′-diphenylene diphosphite, and trilauryl trithiophosphite. Among these, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane and triisodecyl phosphite are preferred.

[0031] The phosphine compound is not particularly limited, but examples thereof include 2,2'-ethylidenebis(4,6-di-tert-butylphenoxy)fluorophosphine, bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphine, biphenyl-4,4'-diylbis[bis(2,4-di-tert-butylphenoxy)phosphine], [(butane-1,1,3-triyl)tris[[2-(1,1-dimethylethyl)-5-methyl-4,1-phenylene]oxy]]tris(ditridecyl phosphonite), 6,6',6''-[nitrilotris(ethyleneoxy)]tris(2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepine), and the like.

[0032] The carbamate compound is not particularly limited, but examples thereof include methylene-bis-dibutyldicarbamic acid, nickel(II) dibutyldithiocarbamate, and the like.

[0033] The benzimidazole compound is not particularly limited, but examples thereof include 2-mercaptobenzimidazole, methyl-2-mercaptobenzimidazole, and the like.

[0034] Among these, from the viewpoint of improving the stability of the ultraviolet absorber, phenolic compounds, sulfur-containing fatty acid compounds, and phosphite compounds are preferred, phenolic compounds and phosphite compounds are more preferred, and phenolic compounds are even more preferred. The stabilizer of the present invention can be used by mixing two or more types of the stabilizer A. When two or more types of the stabilizer A are used by mixing, the stabilizer of the present invention preferably contains a phenolic compound.

[0035] (Stabilizer B) The stabilizer of the present invention preferably further contains a stabilizer B consisting of a hindered amine compound, from the viewpoint of improving the stability of the compound having a sulfide group.

[0036] The hindered amine compound is not particularly limited, but may have the following structure, for example.

[0037]

[0038] In the above formula, R 8 is selected from a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (preferably 1 carbon atom), and an alkoxy group having 1 to 20 carbon atoms; R 9 is an ester group-containing group (preferably an alkyl ester group), and R 10 is a hydrogen atom, and a plurality of structures of the above formula may be contained in one molecule, and may be a repeating unit of a polymer.

[0039] The hindered amine compounds may be used alone or in combination of two or more.

[0040] R in the above formula 8 The hindered amine compound in which is a hydrogen atom is not particularly limited, and examples thereof include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]henicosan-21-one, tetradecyl 2,2,4,4-tetramethyl-21-oxo-3,20-diaza-7-oxadispiro[5.1.11.2]henicosan-20-propanoate, 2,2,6,6-tetramethyl-4-piperidinyl alkanate, and tetradecyl 1,2,3,4-butanetetracarboxylate. Examples thereof include torax(2,2,6,6-tetramethyl-4-piperidinyl), poly[[6-[(1,1,3,3-tetramethylbutyl)amino)-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexadecyl[(2,2,6,6-tetraethyl-4-piperidinyl)imino]), poly[oxy[methyl[3-[(2,2,6,6-tetraethyl-4-piperidinyl)oxy]propyl]silylene]], and 2,2,6,6-tetramethyl-4-piperidinyl methacrylate.

[0041] R in the above formula 8The hindered amine compound in which is a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis[1,2,2,6,6-pentamethyl-4-piperidinyl]2-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-2-butylpropanedioate, tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylic acid, 4,7,N,N'-tetrakis[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, 1,2, Examples of suitable esters include a mixed ester of 3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, 1-[2-(4-hydroxy-2,2,6,6-tetramethylpiperidino)ethyl butanedioate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, and ethylene(2,2,6,6-tetramethylpiperidine-1,4-diyl)bis(4-hydroxy-3,5-di-tert-butylhydrocinnamate). Among these, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate is preferred.

[0042] R in the above formula 8 Examples of the hindered amine compound in which is an alkoxy group having 1 to 20 carbon atoms include, but are not limited to, bis[2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl] decanedioate, bis[2,2,6,6-tetramethyl-1-(undecyloxy)-4-piperidinyl] carbonate, etc. Among these, bis[2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl] decanedioate is preferred.

[0043] Among these, from the viewpoint of improving the stability of the compound having a sulfide group, R 8 When the compound has a benzotriazole skeleton, the alkyl group is preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and more preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms. When the compound has a triazine skeleton, the alkyl group is preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.

[0044] (Compound Having a Sulfide Group) The stabilizer of the present invention is used for compounds having a molecular weight of 1,000 or less and having a sulfide group directly bonded to an aromatic ring or heterocyclic ring.

[0045] The compound having a sulfide group is a compound having a sulfide group and a molecular weight of not more than 1000. The molecular weight of the compound having a sulfide group is preferably not more than 800.

[0046] The compound having a sulfide group is not particularly limited, but examples thereof include compounds having a π-conjugated skeleton containing at least an aromatic ring or a heterocyclic ring. The π-conjugated skeleton containing at least an aromatic ring or a heterocyclic ring is not particularly limited, but examples thereof include compounds having any one skeleton selected from a benzotriazole skeleton, a benzophenone skeleton, a benzoate ester skeleton, a triazine skeleton, and a diphenyl sulfide skeleton. "Having a sulfide group directly bonded to an aromatic ring or a heterocyclic ring" refers to a case where the sulfur atom of the sulfide group is directly bonded to the above-mentioned π-conjugated skeleton, and also includes a case where the sulfide group is directly bonded to an aromatic ring or a heterocyclic ring bonded to the π-conjugated skeleton. The compound having a sulfide group is not particularly limited, but examples thereof include compounds that have the property of absorbing light or electromagnetic waves and are used as ultraviolet absorbers, light absorbers, polymerization initiators, photopolymerization initiators, photosensitizers, raw material monomers for resins, etc. The compound having a sulfide group has good compatibility with organic and inorganic materials that serve as the matrix, can maintain high transparency even when added at a high concentration, exhibits its effects even in a small amount, and has the characteristics of excellent heat resistance, imparting a high refractive index, etc. In order to exhibit such properties, the compound having a sulfide group is preferably one in which the sulfur atom of the sulfide group (—S—) is directly bonded to a carbon atom of any one skeleton selected from the group consisting of a benzotriazole skeleton, a benzophenone skeleton, a benzoate ester skeleton, a triazine skeleton, and a diphenyl sulfide skeleton.

[0047] Examples of the benzotriazole skeleton compound having a heterocyclic ring and an aromatic ring include those represented by the following formula (I).

[0048]

[0049] In the formula, R 1a ~R 9a R each independently represents a group selected from a sulfide group, a hydrogen atom, and a substituent. 1a ~R 9a At least one of the groups is a sulfide group.

[0050] In formula (I), the substituent is not particularly limited, but examples thereof include monovalent or divalent groups selected from hydrocarbon groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, and halogen atoms. Specific examples of these groups include those exemplified in the [Substituents, etc.] section above. When the substituent is a divalent group, R 1a ~R 9a Any two of (preferably two adjacent ones) of these groups combine to form a ring.

[0051] R 1a ~R 9a The positions of the sulfide groups in formula (I) are not particularly limited, but it is preferable that one or two of the R 2a , R 3a , R 5a , R 6a , R 7a , R 8a or R 9a Preferably, R 3a , R 5a , R 6a , R 7a , R 8a or R 9a and more preferably, R 6a , R 7a , R 8a or R 9a and more preferably, R 7a and / or R 8a is.

[0052] In formula (I), R 7a and / or R 8a When R has a sulfide group, R 6a ~R 9a are preferably all hydrogen atoms. 1a ~R 5aPreferred examples of the combinations are as follows: [1] The compound contains one or more substituents selected from a hydrocarbon group having 1 to 18 carbon atoms (including a hydrocarbon group having 2 to 18 carbon atoms, including an alkenyl group and an alkynyl group), a hydroxy group, an aromatic group having 6 to 18 carbon atoms, an ether group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an ester group having 1 to 18 carbon atoms, a (meth)acryloyloxy group, and / or a polyoxyethylene group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 18 carbon atoms in which a hydrogen atom may be substituted, or the base end may be interrupted, or the carbon-carbon bond may be interrupted by such a substituent. [2] In [1], the substituent is at least one selected from a hydrocarbon group having 1 to 10 carbon atoms and a hydroxy group. [3] In [2], the substituent is at least one selected from a hydrocarbon group having 1 to 8 carbon atoms and a hydroxy group. [4] In any of [1] to [3], the hydrocarbon group of the substituent is a linear or branched alkyl group. [5] In [4], the substituent is at least one selected from a methyl group, a t-butyl group, and a hydroxy group. [6] In [5], the substituent is at least one selected from a methyl group, a t-butyl group, and a hydroxy group, and the number of hydroxy groups is one or less. [7] In any of [1] to [6], the number of substituents is 2 to 4. [8] In any of [1] to [7], R 1a ~R 4a and R 1a ~R 5a is a hydrogen atom. [9] In any one of [1] to [8], R 1a , R 2a , R 4a and R 1a ~R 5a is a hydrogen atom.

[10] In [9], R 1a is a hydroxy group, R 2a is a t-butyl group, R 4a is a methyl group, and R 3a , R 5a is a hydrogen atom.

[0053] Examples of compounds having an aromatic benzophenone skeleton include those represented by the following formula (II).

[0054]

[0055] In the formula, R 1b ~R 10b R each independently represents a monovalent group selected from a sulfur-containing group terminated by a sulfide group, a hydrogen atom, and a substituent. 1b ~R 10b At least one of the groups is a sulfur-containing group terminated in a sulfide group.

[0056] In formula (II), the substituent is not particularly limited, and examples thereof include monovalent or divalent groups selected from hydrocarbon groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, and halogen atoms. Specific examples of these groups include those exemplified in the above-mentioned [Substituents, etc.] column. When the substituent is a divalent group, R 1b ~R 10b Any two of (preferably two adjacent ones) of these groups combine to form a ring.

[0057] R 1b ~R 10b The positions of the sulfide groups in formula (II) are not particularly limited, but it is preferable that one or two of the R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b , R 8b , R 9b or R 10b Preferably, R 2b , R 3b , R 4b , R 5b , R 7b , R 8b , R 9b or R 10b and more preferably, R 3b , R 4b , R 8b or R 9b is.

[0058] R 1b ~R 10b The groups other than the sulfide group are not particularly limited, but for example, one of them is a hydroxy group, particularly one of them is a hydroxy group, and the rest are hydrogen atoms. The position of the hydroxy group is not particularly limited, but 1b , R 3b , R 6b , R 8b Examples include:

[0059] Examples of compounds having an aromatic benzoate skeleton include those represented by the following formula (III).

[0060]

[0061] In the formula, R 1c ~R 10c R each independently represents a monovalent group selected from a sulfide group, a hydrogen atom, and a substituent. 1c ~R 10c At least one of the groups is a sulfide group.

[0062] In formula (III), the substituent is not particularly limited, and examples thereof include monovalent or divalent groups selected from hydrocarbon groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, and halogen atoms. Specific examples of these groups include those exemplified in the [Substituents, etc.] section above. When the substituent is a divalent group, R 1c ~R 10c Any two of (preferably two adjacent ones) of these groups combine to form a ring.

[0063] R 1c ~R 10c The positions of the sulfide groups in formula (III) are not particularly limited, but it is preferable that one or two of R 1c , R 2c , R 3c , R 4c , R 5c , R 6c , R 7c , R 8c , R 9c , R 10c Preferably, R2c , R 4c , R 5c , R 6c , R 7c , R 8c , R 9c or R 10c and more preferably, R 5c , R 6c , R 7c , R 8c , R 9c or R 10c and more preferably, R 7c , R 8c or R 9c and particularly preferably R 7c or R 9c It is. 9c When R has a sulfide group, 6c ~R 8c , R 10c are preferably all hydrogen atoms. 1c ~R 5c is not particularly limited, but is, for example, a hydrogen atom or a substituent, and the substituent is at least one selected from a methyl group, a t-butyl group, and a hydroxy group.

[0064] Examples of compounds having an aromatic triazine skeleton include those represented by the following formula (IV).

[0065]

[0066] In the formula, R 1d ~R 15d R each independently represents a monovalent group selected from a sulfide group, a hydrogen atom, and a substituent. 1d ~R 15d At least one of the groups is a sulfide group.

[0067] In formula (IV), the substituent is not particularly limited, and examples thereof include monovalent or divalent groups selected from hydrocarbon groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, and halogen atoms. Specific examples of these groups include those exemplified in the [Substituents, etc.] section above. When the substituent is a divalent group, R 1d ~R 15dAny two of (preferably two adjacent ones) of these groups combine to form a ring.

[0068] R 1d ~R 15d The positions of the sulfide groups in formula (IV) are not particularly limited, but it is preferable that R 1a , R 2a , R 3a , R 5a , R 6a , R 7a , R 8a , R 9a , R 10a , R 11a , R 12a , R 13a , R 14a or R 15a Preferably, R 1a , R 2a , R 3a , R 6a , R 7a , R 8a , R 9a , R 11a , R 12a , R 13a or R 14a and more preferably, R 2a , R 3a , R 7a , R 8a , R 12a or R 13a and more preferably, R 3d , R 8d or R 13d is.

[0069] For example, R 1d ~R 5d , R 6d ~R 10d , and R 11d ~R 15d or R 1d ~R 5d , R 6d ~R 10d , and R 11d ~R 15d or R1d ~R 5d , R 6d ~R 10d , and R 11d ~R 15d All three groups have sulfide groups. In these cases, R 1d ~R 5d , R 6d ~R 10d , and R 11d ~R 15d In the group having a sulfide group, the groups other than the sulfide group are not particularly limited, but for example, one of them is a hydroxy group, and particularly one of them is a hydroxy group and the others are hydrogen atoms.

[0070] Examples of the sulfide group include those represented by the following formula (i):

[0071]

[0072] In the formula, R 1 represents a divalent hydrocarbon group in which a hydrogen atom may be substituted or a carbon atom may be interrupted, and R 2 represents a monovalent hydrocarbon group in which a hydrogen atom may be substituted or a carbon atom may be interrupted, and m represents an integer of 0 to 3, preferably 0 or 1, and more preferably 0. R 1 are each independent when m is 2 or more.

[0073] R 1 , R 2 In the formula (I), the phrase "a hydrogen atom may be substituted or a carbon atom may be interrupted" means that a hydrogen atom of the hydrocarbon is substituted with a monovalent or divalent group, or at least one of the carbon atoms at both ends of the hydrocarbon is interrupted, or the carbon-carbon bond of the hydrocarbon is interrupted.

[0074] The monovalent or divalent group substituting a hydrogen atom or interrupting a carbon atom is not particularly limited, and examples thereof include monovalent or divalent groups selected from unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, and halogen atoms. Specific examples of these include those exemplified in the [Substituents, etc.] section above. In the case of a divalent group, any two (preferably two adjacent) carbon atoms of the hydrocarbon are joined together to form a ring.

[0075] In formula (i), R 1 The divalent hydrocarbon group R preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, even more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms. 1 Examples of the divalent hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, etc. When the divalent hydrocarbon group is formed by substituting a hydrogen atom or interrupting a carbon atom with the monovalent or divalent group, the number of the monovalent or divalent group is not particularly limited, but examples include 2 or less, or 1 or less.

[0076] In the case of the benzotriazole skeleton group represented by formula (I), R 2 is -(R 3 ) n -R 4 Here, R 3 represents a divalent hydrocarbon group having preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, even more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms, which may be substituted with a hydrogen atom or whose carbon atom is interrupted; R 4 represents a substituent containing any one skeleton selected from benzotriazole, benzophenone, benzoic acid ester, and triazine, and n represents an integer of 0 or 1.

[0077] R 4 Among these, examples of the substituent containing benzotriazole include a group represented by the following formula (A), examples of the substituent containing benzophenone include a group represented by the following formula (B), examples of the substituent containing benzoic acid ester include a group represented by the following formula (C), and examples of the substituent containing triazine include a group represented by the following formula (D).

[0078]

[0079] In formula (A), R 16a ~R 24a One of them is R 3 or a monovalent bond to the terminal sulfur atom, and other R 16a ~R 24a each independently represents a hydrogen atom or a substituent.

[0080]

[0081] In formula (B), R 15b ~R 24b One of them is R 3 or a monovalent bond to the terminal sulfur atom, and other R 15b ~R 24b each independently represents a hydrogen atom or a substituent.

[0082]

[0083] In formula (C), R 15c ~R 24c One of them is R 3 or a monovalent bond to the terminal sulfur atom, and other R 15c ~R 24c each independently represents a hydrogen atom or a substituent.

[0084]

[0085] In formula (D), R 20d ~R 22d indicates either [1] or [2] below.

[0086] [1] R 20d ~R 22d At least one of them is R 3 or a monovalent bond to the terminal sulfur atom, and other R 20d ~R 22d are each independently a hydrogen atom, a substituent, or a group represented by the following formula (d):

[0087]

[0088] (In the formula, R 23d ~R 27d each independently represents a hydrogen atom or a substituent. That is, 1 to 3 groups represented by formula (I) may be bonded to the triazine ring. [2] R 20d ~R 22d At least one of the groups is a group represented by the following formula (d'):

[0089]

[0090] (In the formula, R 28d ~R 32d At least one of them is R 3 or a monovalent bond to the terminal sulfur atom, and other R 28d ~R 32d each independently represents a hydrogen atom or a substituent; 20d ~R 22d each independently represents a hydrogen atom or a substituent. That is, the benzene ring represented by formula (d') may have 1 to 5 groups represented by formula (I) bonded thereto.

[0091] R 3 In formulas (A) to (D), (d), and (d'), the group by which a hydrogen atom is substituted or a carbon atom is interrupted is not particularly limited, and examples thereof include monovalent or divalent groups selected from hydrocarbon groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, and halogen atoms. In formulas (A) to (D), (d), and (d'), the substituent is not particularly limited, and examples thereof include monovalent or divalent groups selected from hydrocarbon groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, and halogen atoms. Specific examples of these include those exemplified in the above column under "Substituents, etc." When a hydrogen atom is substituted with a divalent group, the two carbon atoms (preferably two adjacent carbon atoms) bonded together form a ring.

[0092] More specifically, in formula (i), R 2 Examples of the group include a group represented by the following formula (j).

[0093]

[0094] In the above formula, X represents a divalent aliphatic hydrocarbon group in which a hydrogen atom may be substituted, Y represents a divalent aromatic hydrocarbon group or alicyclic hydrocarbon group in which a hydrogen atom may be substituted, and Z represents a divalent heteroatom-containing group Z selected from a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, and a phosphorus-containing group. 1 or a divalent heteroatom Z selected from an oxygen atom and a sulfur atom; 2 where o, p, and q represent integers of 0 or more. o X's, p Y's, and q Z's are independent of each other, and the order of X, Y, and Z is arbitrary. In one example, when at least one of X, Y, and Z is two or more, X's, Y's, and Z's are not adjacent to each other. At least one of o and p is an integer of 1 or more.

[0095] The divalent aliphatic hydrocarbon group X has 1 to 20, preferably 1 to 12, carbon atoms, and examples thereof include linear or branched alkylene groups, linear or branched alkenylene groups, and linear or branched alkynylene groups. Specific examples include, but are not limited to, methylene group, ethane-1,2-diyl group, propane-1,3-diyl group, 1-methylethane-1,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, pentane-1,5-diyl group, pentane-1,4-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nona Examples of such groups include decane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-yl group, tetradecane-1,14-yl group, pentadecane-1,15-yl group, hexadecan-1,16-yl group, heptadecane-1,17-yl group, octadecane-1,18-yl group, nonadecan-1,19-yl group, and eicosan-1,20-yl group. Among these, aliphatic hydrocarbon groups in which no hydrogen atoms are substituted are preferred, alkylene groups are more preferred, and linear alkylene groups are even more preferred.

[0096] Of the divalent aromatic hydrocarbon groups or alicyclic hydrocarbon groups Y, the aromatic hydrocarbon group has a carbon number of 6 to 18, preferably 6 to 14. The aromatic hydrocarbon group contains an aromatic ring such as a benzene ring, a naphthalene ring, or an anthracene ring, and a hydrogen atom of the aromatic ring may be substituted with an aliphatic hydrocarbon group or the like. Specific examples include, but are not limited to, phenylene groups (1,4-phenylene, 1,3-phenylene, 1,2-phenylene, etc.), naphthylene groups (1,8-naphthylene, 2,7-naphthylene, 2,6-naphthylene, 1,4-naphthylene, 1,3-naphthylene, etc.), anthracenylene groups (9,10-anthracenylene, 1,8-anthracenylene, 2,7-anthracenylene, 2,6-anthracenylene, 1,4-anthracenylene, 1,3-anthracenylene, etc.), etc. Among these, aromatic hydrocarbon groups in which no hydrogen atoms are substituted are preferred, and phenylene groups are more preferred.

[0097] Of the divalent aromatic hydrocarbon groups or alicyclic hydrocarbon groups Y, the alicyclic hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms. It may contain an aliphatic ring, and a hydrogen atom of the aliphatic ring may be substituted with an aliphatic hydrocarbon group or the like. Specific examples include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group (1,4-cyclohexylene group, 1,3-cyclohexylene group, 1,2-cyclohexylene, etc.), a cycloheptylene group, a cyclooctylene group, etc. Among these, an alicyclic hydrocarbon group in which a hydrogen atom is not substituted is preferred, and a cyclohexylene group is more preferred.

[0098] Among Z, a divalent heteroatom-containing group Z 1 is selected from a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, and a phosphorus-containing group, and examples thereof include those exemplified in the above-mentioned [Substituent, etc.] column, and a nitrogen-containing group or an oxygen-containing group having a double bond is more preferred.

[0099] A divalent group Z having a double bond 1 Examples of the substituent include divalent groups having a double bond among those exemplified in the above column of [Substituents, etc.].

[0100] Examples of the divalent nitrogen-containing group having a double bond include an amide group, a urea group, a urethane group, an imide group, a carbodiimide group, an azo group, a pyridine group, an imidazole group, a toluidine group, and a nitroalkyl group.

[0101] Examples of the divalent oxygen-containing group having a double bond include a carboxy group, a carbonyl group, an ester group, an oxazole group, a carbamate group, and a carbamoyl group.

[0102] Examples of the divalent sulfur-containing group having a double bond include a thioester group, a thioamide group, a sulfonyl group, a sulfoxide group, a thiocarbonyl group, a thiourea group, a thiocarbamate group, a dithiocarbamate group, a thiophene group, and a thiazole group.

[0103] Examples of the divalent phosphorus-containing group having a double bond include a phosphate ester group and a phosphonate ester group.

[0104] In addition, among Z, a divalent heteroatom Z 2 is an oxygen atom, a sulfur atom, etc., and is preferably an oxygen atom.

[0105] Examples of the substituent with which a hydrogen atom of the divalent aliphatic hydrocarbon group X, or the divalent aromatic hydrocarbon group or alicyclic hydrocarbon group Y may be substituted include an unsaturated group, a nitrogen-containing group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, and a halogen atom, and specific examples of these include those exemplified in the above-mentioned column of [Substituent, etc.].

[0106] When a hydrogen atom of the divalent aliphatic hydrocarbon group X, the divalent aromatic hydrocarbon group, or the alicyclic hydrocarbon group Y is substituted, the number of substituents is not particularly limited, but examples include 2 or less, or 1 or less.

[0107] In formula (j), when a divalent aliphatic hydrocarbon group X is contained, o is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1. p is preferably 0 to 2, more preferably 0 to 1, and even more preferably 0. q is preferably 0 to 2, more preferably 0 to 1, and even more preferably 0. Preferred examples of formula (j) include -X-H, -X-Y-H, -Y-X-H, -X-Z-H, -X-Z-X-H, -X-Z-Y-H, and -Y-Z-X-H.

[0108] In formula (j), when a divalent aromatic hydrocarbon group or alicyclic hydrocarbon group Y is contained, p is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1. o is preferably 0 to 2, and more preferably 0 to 1. q is preferably 0 to 2, more preferably 0 to 1, and even more preferably 0. Preferred examples of formula (j) include -Y-H, -Y-X-H, -X-Y-H, -Y-Z-H, -Y-Z-Y-H, -Y-Z-X-H, and -X-Z-Y-H.

[0109] In formula (j), the number q of Z is preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 to 1.

[0110] In a preferred example of formula (j), R 2 has a divalent aliphatic hydrocarbon group X in which no hydrogen atom is substituted. In this case, in a preferred example, R 2 In another preferred example, p and q are 0. 2 has a divalent aromatic hydrocarbon group or alicyclic hydrocarbon group Y in which no hydrogen atom is substituted. In this case, in a preferred example, R 2 In all of these cases, p is 1, q is 0, and o is 0 or 1. In one preferred example, R 2 In this case, q is 1 or 2. In a preferred example, R 2 is a divalent hetero element-containing group Z selected from a nitrogen-containing group and an oxygen-containing group; 1 It has.

[0111] In a preferred example of formula (j), R 2 where o has 1 to 4 divalent aliphatic hydrocarbon groups X. In this case, in a preferred example, R2 has one or two o's.

[0112] In a preferred example of formula (j), R 2 and p has 1 to 4 divalent aromatic hydrocarbon groups or alicyclic hydrocarbon groups Y. In this case, in a preferred example, R 2 In the formula, p is 1 or 2.

[0113] In a preferred example of formula (j), R 2 q is 1 to 4 divalent heteroatom-containing groups Z selected from the group consisting of a divalent nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, and a phosphorus-containing group; 1 In this case, in a preferred example, R 2 In the formula, q is 1 or 2.

[0114] In a preferred example of formula (j), R 2 where o is 1 to 4 divalent aliphatic hydrocarbon groups X, and p is 1 to 4 divalent aromatic hydrocarbon groups or alicyclic hydrocarbon groups Y. In this case, in a preferred example, R 2 has one or two o's and one or two p's.

[0115] In a preferred example of formula (j), R 2 q is a divalent heteroatom-containing group Z selected from the group consisting of a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, and a phosphorus-containing group; 1 In this case, in a preferred example, R 2 In the formula, p is 1 or 2 and q is 1 or 2.

[0116] In a preferred example of formula (j), R 2 p is 1 to 4 divalent aromatic hydrocarbon group or alicyclic hydrocarbon group Y, and q is 1 to 4 divalent hetero element-containing group Z selected from divalent nitrogen-containing groups, oxygen-containing groups, sulfur-containing groups and phosphorus-containing groups. 1 In this case, in a preferred example, R 12 represents one or two o's and one or two q's.

[0117] In a preferred example of formula (j), R 2o is 1 to 4 divalent aliphatic hydrocarbon group X, p is 1 to 4 divalent aromatic hydrocarbon group or alicyclic hydrocarbon group Y, and q is 1 to 4 divalent hetero element-containing group Z selected from divalent nitrogen-containing groups, oxygen-containing groups, sulfur-containing groups and phosphorus-containing groups. 1 In this case, in a preferred example, R 2 represents 1 or 2 o's, 1 or 2 p's, and 1 or 2 q's.

[0118] In formula (j), R 2 However, when o has 1 to 4 divalent aliphatic hydrocarbon groups X, X has 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 7 carbon atoms.

[0119] In formula (j), R 2 However, when p has 1 to 4 divalent aromatic hydrocarbon groups or alicyclic hydrocarbon groups Y, Y preferably has 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms.

[0120] In formula (j), R 2 However, when o has 1 to 4 divalent aliphatic hydrocarbon groups X and p has 1 to 4 divalent aromatic hydrocarbon groups or alicyclic hydrocarbon groups Y, the number of carbon atoms in X is preferably 1 to 12, more preferably 1 to 7, and the number of carbon atoms in Y is preferably 6 to 20, more preferably 6 to 14.

[0121] In a preferred example of formula (j), R 2 q is a divalent heteroatom-containing group Z selected from the group consisting of a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, and a phosphorus-containing group; 1 When the group has the formula (I), preferably, o is 1 to 2 and q is 1 to 2, more preferably, o is 2 and q is 1, or o is 1 and q is 2, and even more preferably, o is 1 and q is 1.

[0122] In a preferred example of formula (j), R 2 p is 1 to 4 divalent aromatic hydrocarbon group or alicyclic hydrocarbon group Y, and q is 1 to 4 divalent hetero element-containing group Z selected from divalent nitrogen-containing groups, oxygen-containing groups, sulfur-containing groups and phosphorus-containing groups. 1In this case, preferably, p is 1 to 2 and q is 1 to 2, more preferably, p is 2 and q is 1, or p is 1 and q is 2, and even more preferably, p is 1 and q is 1.

[0123] <Composition> The composition of the present invention contains the stabilizer and a compound having a sulfide group directly bonded to an aromatic ring or heterocycle and having a molecular weight of not more than 1000. The stabilizer may be stabilizer A or stabilizers A and B.

[0124] The index of improved stability of the compound having a sulfide group in the composition of the present invention is not particularly limited, but for example, the difference in transmittance at a specific wavelength in the ultraviolet-visible transmission spectrum of the compound having a sulfide group can be used as an index. When the compound having a sulfide group is decomposed or modified by light, the ultraviolet-visible transmission spectrum changes, and therefore, it can be said that the smaller the difference in transmittance at a specific wavelength before and after a stability test, the more excellent the stability.

[0125] For example, in the case of a compound having a benzotriazole skeleton, light with a wavelength of 300 to 400 nm is irradiated at an illuminance of 80 W / m 2 After 100 hours or 500 hours of irradiation, the difference in transmittance at 380 nm is preferably 60% or less, more preferably 40% or less, even more preferably 30% or less, particularly preferably 20% or less, especially preferably 10% or less, and most preferably 5% or less. Under the same conditions, the difference in transmittance at 390 nm is preferably 60% or less, more preferably 40% or less, even more preferably 30% or less, particularly preferably 20% or less, especially preferably 10% or less, and most preferably 5% or less. Under the same conditions, the difference in transmittance at 400 nm is preferably 45% or less, more preferably 30% or less, even more preferably 20% or less, especially preferably 10% or less, and especially preferably 5% or less.

[0126] For example, in the case of a compound having a triazine skeleton, light with a wavelength of 300 to 400 nm is irradiated at an illuminance of 80 W / m 2After 100 hours of irradiation at 1000 nm, the decrease in transmittance at 400 nm is preferably 40% or less, more preferably 30% or less, even more preferably 20% or less, particularly preferably 10% or less, especially preferably 5% or less, and most preferably 1% or less. Under the same conditions, the decrease in transmittance at 410 nm is preferably 50% or less, more preferably 30% or less, even more preferably 20% or less, particularly preferably 10% or less, especially preferably 5% or less, and most preferably 1% or less. Under the same conditions, the decrease in transmittance at 420 nm is preferably 30% or less, more preferably 20% or less, even more preferably 10% or less, especially preferably 5% or less, and especially preferably 1% or less.

[0127] In the composition of the present invention, the mass ratio of the compound having a sulfide group to stabilizer A is not particularly limited, but is preferably 10:1 to 1:10, more preferably 5:1 to 1:5, and even more preferably 1:1.

[0128] When the composition of the present invention contains stabilizer B, the mass ratio of the compound having a sulfide group to stabilizer B is not particularly limited, but is preferably 10:1 to 1:10, more preferably 5:1 to 1:5, and even more preferably 1:1.

[0129] The composition of the present invention may contain other components in addition to those described above, provided that the effects of the composition are not impaired.

[0130] In the composition of the present invention, the total amount of the sulfide group-containing compound, stabilizer A, and, if present, stabilizer B is not particularly limited, but is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total amount of the composition. <Additive for Organic and / or Inorganic Material Compositions> The composition of the present invention can be used as an additive for organic and / or inorganic material compositions. This additive is useful not only for preventing the reduction in the above-mentioned effects by improving the stability of the sulfide group-containing compound, but also for preventing the deterioration of organic and inorganic materials due to ultraviolet light by improving the stability of the sulfide group-containing compound, and for preventing the reduction in the functionality of the organic and inorganic materials. For example, in the case of a resin composition containing the composition of the present invention, the deterioration and decomposition of the resin due to ultraviolet light can be suppressed, thereby preventing the reduction in the effects of the resin. For the organic and / or inorganic material composition, see the description in the "Organic and / or Inorganic Material Compositions" section below.

[0131] The form of the additive of the present invention is not particularly limited, but for example, a mixture of the compound having a sulfide group and the stabilizer can be prepared in advance and added to the resin, or the compound having a sulfide group and the stabilizer can be added separately to the resin. Of these, the former mixture encompasses the composition of the present invention.

[0132] In the additive of the present invention, the mass ratio of the compound having a sulfide group to stabilizer A is not particularly limited, but is preferably 10:1 to 1:10, more preferably 5:1 to 1:5, and even more preferably 1:1.

[0133] When the additive of the present invention contains stabilizer B, the mass ratio of the compound having a sulfide group to stabilizer B is not particularly limited, but is preferably 10:1 to 1:10, more preferably 5:1 to 1:5, and even more preferably 1:1.

[0134] The additive of the present invention may contain other components in addition to those described above, provided that the effects of the additive are not impaired.

[0135] In the additive of the present invention, the total amount of the compound having a sulfide group, stabilizer A, and stabilizer B, if blended, is not particularly limited, but is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total amount of the additive.

[0136] <Organic and / or inorganic material composition> The additive of the present invention can be used as an organic and / or inorganic material composition further containing an organic and / or inorganic material as a matrix. The compound having a sulfide group used in the present invention has high affinity, compatibility, and adhesion with various organic and inorganic materials, and when this ultraviolet absorber is mixed, dissolved, dispersed, applied, or coated, a homogeneous composition or member can be obtained, and when a transparent member is used, a member with excellent transparency can be obtained.

[0137] The shape of the organic material and / or inorganic material composition is not particularly limited, and examples thereof include a coating film, a coated film, a laminated film, a film, a sheet, a plate, a powder, a granule, a pellet, a tablet, a molded product, and the like.

[0138] The organic material and / or inorganic material composition containing the compound having a sulfide group used in the present invention can be an organic material and / or inorganic material composition that efficiently absorbs harmful light in a wavelength region of 380 to 420 nm while suppressing yellowing, has excellent appearance, does not bleed out the ultraviolet absorber, and is free from discoloration, deterioration in ultraviolet absorption ability, and deterioration in transparency over a long period of use, and is therefore excellent not only in stability but also in heat resistance.

[0139] The organic material and / or inorganic material composition may be any of an organic material composition, an inorganic material composition, and an organic-inorganic material composition. Here, the organic-inorganic material composition refers to the organic material composition described above that contains an inorganic material as a material other than the organic material, or the inorganic material composition described above that contains an organic material as a material other than the inorganic material.

[0140] The organic material is not particularly limited, but examples thereof include organic resins, materials derived from animals and plants, materials derived from crude oil, organic compounds, and the like.

[0141] The organic resin is not particularly limited, and a wide variety of conventionally known resins can be used, including thermoplastic resins and thermosetting resins, each of which includes polymers having one type of repeating unit and copolymers having multiple repeating units.

[0142] The thermoplastic resin is not particularly limited, but examples thereof include polymers such as (meth)acrylic resins, olefin resins, styrene resins, ester resins, ether resins, vinyl chloride resins, fluorine resins, vinyl resins, polycarbonate resins, polyamide resins, polyimide resins, polyamideimide resins, polymaleimide resins, polyvinylpyrrolidone resins, polyurethane resins, and polysulfone resins, and copolymers such as butadiene-styrene copolymers, acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, styrene-isoprene copolymers, styrene-acrylic acid copolymers, and vinyl chloride-vinylidene chloride-acrylonitrile copolymers. These may be used alone or in combination of two or more.

[0143] The thermosetting resin is not particularly limited, but examples thereof include polymers such as phenolic resins, urea resins, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, and episulfide resins, and copolymers such as acrylic melamine resins and acrylic urethane resins. These may be used alone or in combination of two or more.

[0144] The inorganic material is not particularly limited, but examples thereof include siliceous materials produced by a sol-gel method, glass, water glass, low-melting-point glass, quartz, silicon resin, alkoxysilane, silane coupling agent, metal, metal oxide, mineral, inorganic compound, etc. The glass is not particularly limited, but examples thereof include silicon oxide, alkali-free glass, soda glass, etc.

[0145] The content of the additive of the present invention in the organic material and / or inorganic material composition of the present invention is not particularly limited, but is, for example, preferably 0.001 to 50 mass %, more preferably 0.01 to 20 mass %, and even more preferably 0.1 to 10 mass %.

[0146] The organic material and / or inorganic material composition of the present invention may contain other components in addition to those described above, provided that the effects of the composition are not impaired. Examples of such other components include, but are not limited to, antioxidants, heat stabilizers, weather stabilizers, light stabilizers, pigments, dyes, fillers, plasticizers, antistatic agents, nucleating agents, wetting agents, preservatives, antifungal agents, antifoaming agents, stabilizers, antioxidants, and chelating agents.

[0147] <Method for Improving Stability> The method for improving the stability of a compound having a sulfide group directly bonded to an aromatic ring or heterocycle and having a molecular weight of 1,000 or less according to the present invention is characterized in that the compound having a sulfide group and a stabilizer A are added to a composition so that they coexist in the composition. In the method of the present invention, a stabilizer B may also be added to the composition.

[0148] Combining the compound having a sulfide group with stabilizer A can improve stability, and using stabilizer B in combination further improves stability. The compound having a sulfide group decomposes over time, resulting in a decrease in its ultraviolet absorption ability, leaving room for improvement in stability. It has been generally known to use additives such as ultraviolet absorbers to stabilize resins, but in the present invention, stabilizer A or a combination of stabilizer A and stabilizer B is effective in improving the stability of the compound having a sulfide group itself.

[0149] The present invention will be described in detail below using examples, but the present invention is not limited to these examples. 1. Compounds having a sulfide group directly bonded to an aromatic ring or heterocycle with a molecular weight of 1,000 or less Compounds 1 to 3 and 9 were synthesized by the method described in WO 2016 / 021664. Compounds 4 to 8 were synthesized by the method shown below.

[0150]

[0151] 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (6.85 g, 21.7 mmol), 3-mercapto-1-propanol (3.00 g, 32.5 mmol), potassium carbonate (6.60 g, 47.7 mmol), and potassium iodide (0.25 g, 1.52 mmol) were heated and stirred in 30 mL of DMF at 135-140°C for 8 hours. After completion of the reaction, the pH was adjusted, filtered, washed with MeOH, and recrystallized to obtain Intermediate 1 as a pale yellow solid. Intermediate 1 (3.00 g, 8.08 mmol), lauric acid (2.42 g, 12.11 mmol), and p-toluenesulfonic acid (0.15 g, 0.81 mmol) were reacted in 50 mL of toluene at 80-90°C for 18 hours with stirring. After the reaction was completed, Kyoward 500 was added and the mixture was stirred for 1 hour, filtered, and the filtrate was evaporated to obtain a yellow crude product, which was then recrystallized to synthesize Compound 4 as a pale yellow solid. The physical properties are shown below. FT-IR (KBr): 2918 cm -1 :OH stretching vibration, 1740cm -1 :C=O stretching vibration, 1453, 1392cm -1 : Triazole ring stretching vibration 1 H-NMR (CDCl3 400MHz): δ 0.87 (t, 3H, CH3CH2 -), 1.29 (m, 18H, CH3(CH2)9CH2-), 1.54 (S, 9H, -Ph-OH-CH3-C(CH3)3), 1.63 (m, 2H, -CH2-C(=O)-O-), 2.06 (quin, 2H, -O-CH2CH2CH2-S-), 2.39 (s, 3H, -Ph-OH-CH3-C(CH3)3), 2.33 (t, 2H, -O-CH2CH2CH2-S-), 3.11 (t, 2H, -O-CH2CH2CH2-S-), 7.17 (s, 1H), 7.40 (d, 1H), 7.76 (s, 1H), 7.81 (d, 1H), 8.05 (S, 1H), (insg.5arom. CH), 11.58 (s, 1H, -Ph-OH-CH3-C(CH3)3) 13 C-NMR (CDCl3 400MHz): δ 14.1 (CH3(CH2) 10 C(=O)-O-), 20.9 (-Ph-OH-CH3-C(CH3)3), 22.7 (CH3CH2CH2(CH2)6C(=O)-O-), 25.0 (-Ph-OH-CH3-C(CH3)3), 28.0~29.9 (CH3(CH2)2(CH2)8C(=O)-O-), 29.5 (-Ph-OH-CH3-C(CH3)3) , 31.9 (CH3CH2CH2(CH2)8C(=O)-O-), 34.3 (CH3(CH2) 10 C(=O)-O-CH2CH2CH2-S), 35.4 (CH3(CH2) 10 C(=O)-O-(CH2)2CH2-S), 62.5 (CH3(CH2) 10 C(=O)-O-CH2(CH2)2-S), 114.6, 117.8, 119.3, 128.3, 128.7 (CH arom ), 125.4, 141.4, 143.4 (C arom ), 129.4 (C arom -CH3), 136.9(C arom -S), 139.1 (C arom -C(CH3)3), 146.7 (C arom -OH), 173.8 (CH3(CH2) 10 C(=O)-O-)

[0152] Hydroxybenzenethiol (15.0 g, 118.8 mmol), bromooctadecane (37.63 g, 112.8 mmol), and potassium carbonate (24.6 g, 178.2 mmol) were heated to reflux in 150 mL of acetonitrile for 6 hours. After the reaction was completed, toluene was added, and the mixture was washed with water, evaporated, and purified with a column to obtain intermediate 2 as a liquid. Salicylic acid (8.8 g, 63.9 mmol) and thionyl chloride (22.8 g, 191.6 mmol) were reacted at 25°C for 3 hours, after which unreacted thionyl chloride was evaporated under reduced pressure to obtain intermediate salicylic acid chloride (9.8 g, 62.6 mmol). The obtained salicylic acid chloride (2.50 g, 16.0 mmol), intermediate 2 (6.95 g, 18.35 mmol), and potassium carbonate (2.20 g, 15.91 mmol) were reacted in 100 mL of toluene under reflux for 12 hours. After the reaction was completed, toluene was added, the mixture was washed with water, the solvent was distilled off, and the mixture was purified with a column to obtain compound 5. FT-IR (KBr): 3228 cm -1 : OH stretching vibration, 1683cm -1 :C=OO stretching vibration, 592cm -1 :CS stretching vibration 1 H-NMR (CDCl3 400MHz): δ0.87 (t, 3H, CH3CH2 - ), 1.25 (m, 28H, CH3(CH2) 14 CH2CH2CH2-),1.43 (m, 2H, CH3(CH2) 14 CH2CH2CH2-),1.67 (quin, 2H, CH3(CH2) 14 CH2CH2CH2-),2.94 (t, 2H, CH3(CH2) 14 CH2CH2CH2-),6.97 (m, 2H), 7.05 (d, 1H), 7.14 (s, 1H), 7.24 (d, 1H), 7.34 (t, 1H), 7.54 (t, 1H), 8.05 (d, 1H), (insg.8arom. CH), 10.46 (s, 1H, -Ph-OH) 13C-NMR (CDCl3 400MHz): δ14.1 (CH3(CH2) 17 -S), 22.7 (CH3CH2(CH2) 16 -S), 28.8 (CH3CH 2CH2(CH2) 15 -S), 29.2~33.3 (CH3CH 2CH2(CH2) 15 -S), 111.8, 118.6, 119.5, 126.1, 129.7, 130.3, 136.6 (CH arom ), 117.9 (C arom -C(=O)-O-), 139.5(C arom -S), 150.4(-(O=)COC arom ), δ162.3(C arom -OH), δ168.8 (C(=O)-)

[0153] 5-Chloro-2-hydroxybenzophenone (5.0 g), benzenethiol (2.8 g), potassium carbonate (6.5 g), potassium iodide (0.3 g), and DMF (10 g) were added and stirred under heating at 135°C for 6 hours. After the reaction, ethyl acetate, water, and hydrochloric acid were added and the organic layer was recovered, then washed with water and distilled off. The obtained crude product was purified by column chromatography and recrystallization to obtain Compound 6 as a white solid. FT-IR (KBr): 3168 cm -1 : OH stretching vibration, 1644cm -1 : C=O stretching vibration, 571cm -1 : CS stretching vibration 1 H-NMR (CDCl3 400MHz): δ 7.09 (d, 1H), 7.17 (m, 3H), 7.26 (t, 2H), 7.46 (t, 2H), 7.56-7.72 (m, 4H), 7.72 (d, 1H), (insg.13arom. CH), 12.10 (s, 1H, -Ph-OH) 13 C-NMR (CDCl3 400MHz): δ132.3, 129.2, 129.2, 129.0, 128.5, 126.4, 123.4 , 119.8, 119.8 (CH arom), 137.4, 137.3 (-C(=O)-Carom-SC arom ), 138.4(C arom -C(=O)), 141.3(-(O=)CC arom -OH-S-), δ 163.3(C arom -OH), δ 201.0 (C(=O)-)

[0154] 4,4'-Dichlorobenzophenone (5.0 g), potassium carbonate (12 g), potassium iodide (1.0 g), and DMF (15 g) were added, mixed, and stirred. p-Isopropylbenzenethiol (7.3 g) was added, and the mixture was heated at 110°C for 12 hours. After that, the mixture was cooled to 70°C, ion-exchanged water was added, and the mixture was further cooled to room temperature. After cooling, the precipitated solid was separated, heated and dissolved in toluene at 80°C, and a 37% aqueous hydrogen chloride solution was added, followed by heating for 15 minutes. The aqueous layer was then separated, and the toluene solution was washed with water. Methanol was added to the toluene solution, and recrystallization was carried out to obtain Compound 7. IR (KBr): 2960 cm -1 , 2360 cm -1 , 1652 cm -1 , 1586 cm -1 , 1486 cm -1 , 1285 cm -1 , 1079 cm -1 , 827 cm -1 , 753 cm -1 1 HNMR (CDCl3, 400 MHz): 1.27-1.28 (d, 6H, Me), 2.91-2.98 (m, 1H, -CHMe2), 7.17-7.19 (d, 2H, Ph), 7.26-7.28 (d, 2H, Ph), 7.43-7.46 (d, 2H, Ph), 7.63-7.65 (d, 2H,Ph). 13 CNMR (CDCl3, 100 MHz): 23.7 (Me), 34.1 (-CHMe2), 126.5, 127.9, 128.4, 130.5, 134.3, 134.6, 150.0, 197.8 (Ph)

[0155] ​4,4'-Dichlorobenzophenone (5.0 g), potassium carbonate (12 g), potassium iodide (1.0 g), and DMF (15 g) were added, mixed, and stirred. p-tert-butylbenzenethiol (8.0 g) was added, and the mixture was heated at 110°C for 12 hours. After that, the mixture was cooled to 70°C, ion-exchanged water was added, and the mixture was further cooled to room temperature. After cooling, the precipitated solid was separated, heated and dissolved in toluene at 80°C, and a 37% aqueous hydrogen chloride solution was added, followed by heating for 15 minutes. The aqueous layer was then separated, and the toluene solution was washed with water. Methanol was added to the toluene solution, and recrystallization was carried out to obtain compound 8. IR (KBr): 2959 cm -1 , 2360 cm -1 , 1644 cm -1 , 1587 cm -1 , 1309 cm -1 , 1287 cm -1 , 834cm -1 . 1 HNMR (CDCl3, 400 MHz): 1.34 (s, 9H, -CMe3), 7.18-7.20 (d, 4H, Ph), 7.43-7.45 (d, 8H, Ph), 7.63-7.65 (d, 4H, Ph) 13 CNMR (CDCl3, 100 MHz): 31.1 (Me), 34.8 (-CMe3), 126.5, 127.0, 128.2, 130.4, 133.8, 134.6, 144.8, 152.4 (Ph), 194.9 (C=O)

[0156] 2. Stabilizers Stabilizers A-1, A-3 to A-7 and stabilizer B-1 were reagents manufactured by Tokyo Chemical Industry Co., Ltd., stabilizer B-2 was a reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., and stabilizer A-2 was a reagent manufactured by BASF Japan Ltd.

[0157] Compound A-1: ​​Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] Compound A-2: N,N'-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl tert-4-hydroxyphenyl)propanamide] Compound A-3: Pentaerythritol tetrakis[3-laurylthiopropionate] Compound A-4: 3,3'-thiodipropionic acid didodecyl compound A-5: 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Compound A-6: Triisodecyl phosphite (mixture of isomers) Compound A-7: 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate Compound B-1: bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate Compound B-2: bis[2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl] decanedioate

[0158] 3. Evaluation of Stability After preparing 0.005 wt % toluene solutions of the compounds 1 to 8 having a sulfide group, stabilizers A (A-1 to A-6) were added to the compounds having a sulfide group so that the mass ratio was 1:1 relative to the compounds having a sulfide group, and also so that the mass ratios of the compounds having a sulfide group, stabilizers A, and stabilizer B were 1:1:1, and so that the mass ratios of the compounds having a sulfide group and stabilizer A (two types) were 1:1:1, to prepare test solutions.

[0159] The ultraviolet-visible transmittance spectrum of the test solution was measured using an ultraviolet-visible infrared spectrophotometer (UH4150V manufactured by Hitachi High-Tech Science), and the initial (before irradiation) ultraviolet transmittance (%): A was read at 380, 390, and 400 nm for the test solution mixed with compound 1, 2, or 4; at 400, 410, and 420 nm for the test solution mixed with compound 3; at 300, 310, and 320 nm for the test solution mixed with compound 5, 7, or 8; and at 350, 360, and 370 nm for the test solution mixed with compound 6.

[0160] Thereafter, the toluene in the test solution was distilled off under reduced pressure to dry it, and the test solution was exposed to ultraviolet light at a wavelength of 300 to 400 nm and an illuminance of 80 W / m using an ultraviolet irradiator (Atlas Weatherometer Ci3000+w). 2 The dried samples were irradiated with ultraviolet light under the condition of a black panel temperature of 63°C, and after 100 hours of irradiation for Compounds 1, 3, 4, 5, 6, 7, and 8, and after 500 hours of irradiation for Compound 2, toluene solutions of the same concentrations as above were prepared and measured for ultraviolet-visible transmission spectra. The transmittance (%): B was read at 380, 390, and 400 nm for Compound 1, 2, or 4, at 400, 410, and 420 nm for Compound 3, at 300, 310, and 320 nm for Compound 5, 7, or 8, and at 350, 360, and 370 nm for Compound 6, and the difference in transmittance before and after irradiation, ΔT: B - A (%), was calculated (Tables 1 to 4).

[0161] As can be seen from Table 1, when the compound having a sulfide group is Compound 1, the compositions containing a stabilizer (Examples 1 to 15) showed a small difference in transmittance before and after irradiation at any measurement wavelength, as compared with Comparative Example 1 which did not contain a stabilizer, and were therefore confirmed to be excellent in stability.

[0162] Among the compositions containing stabilizer A and the compound having a sulfide group (Examples 1, 3, 5, 8, 11, 12, and 15), the compositions in which stabilizer A was a phenolic compound (Examples 1, 3, and 15) showed smaller differences in transmittance before and after irradiation at all measurement wavelengths (380 nm: 20% or less, 390 nm: 30% or less, and 400 nm: 10% or less) than the compositions in which stabilizer A was a sulfur-containing fatty acid compound or a phosphite ester compound, and were therefore more stable. The use of two types of stabilizer A in combination provided better stability than the use of either alone (Example 15).

[0163] The use of stabilizer A and stabilizer B (Examples 2, 4, 6, 7, 9, 10, 13, and 14) resulted in superior stability compared to the use of stabilizer A alone (Examples 1, 3, 5, 8, 11, and 12). In particular, the compositions containing stabilizer A (sulfur-containing fatty acid compound, phosphite ester compound) and stabilizer B (Examples 6, 7, 9, 10, 13, and 14) showed smaller differences in transmittance before and after irradiation (380 nm: 3% or less, 390 nm: 5% or less, 400 nm: 6% or less) than the use of stabilizer A alone (Examples 5, 8, 11, and 12), demonstrating superior stability.

[0164] From Table 2, it was confirmed that when the compound having a sulfide group was Compound 2, the composition containing a stabilizer (Example 16) had a small difference in transmittance before and after irradiation at any measurement wavelength, and was therefore excellent in stability, as compared with Comparative Example 2 which did not contain a stabilizer.

[0165] As can be seen from Table 3, when the compound having a sulfide group is Compound 3, the compositions containing a stabilizer (Examples 17 to 30, 42 to 44) showed a small difference in transmittance before and after irradiation at all measurement wavelengths, and were confirmed to have excellent stability, compared to Comparative Example 3 which did not contain a stabilizer. The use of two types of stabilizer A in combination resulted in superior stability compared to the use of either compound alone (Examples 42 to 44), and among these, the combination of a phenolic compound and a phosphite ester compound was particularly stable (Example 44).

[0166] Among the compositions containing stabilizer A (Examples 17, 19, 21, 24, 27, and 28), the compositions in which stabilizer A was a phenolic compound (Examples 17 and 19) had a smaller difference in transmittance before and after irradiation at all measurement wavelengths (400 nm: 20% or less, 410 nm: 10% or less, 420 nm: 10% or less) than the compositions in which stabilizer A was a sulfur-containing fatty acid compound or a phosphite ester compound, and were therefore more stable.

[0167] The use of stabilizer A and stabilizer B (Examples 18, 20, 22, 23, 25, 26, 29, 30) was more stable than the use of stabilizer A alone (Examples 17, 19, 21, 24, 27, 28). In particular, the compositions containing stabilizer A (sulfur-containing fatty acid compound, phosphite ester compound) and stabilizer B (Examples 22, 23, 25, 26, 29, 30) had a smaller difference in transmittance before and after irradiation (400 nm: 1% or less, 410 nm: 5% or less, 420 nm: 5% or less) than the composition containing stabilizer A alone (Examples 21, 24, 27, 28), and were therefore excellent in light resistance. Furthermore, the stabilizer A was a phosphite ester compound, and the R of stabilizer B was 8 It was confirmed that when is an alkoxy group, the difference in transmittance before and after irradiation is 1% or less at any measurement wavelength, and the stability is remarkably excellent.

[0168] Using the same test method as above, stability evaluation tests were also conducted on Compounds 4 to 8. The results are shown in Table 4. As can be seen from Table 4, when the compound having a sulfide group is Compounds 4, 5, 6, 7, or 8, the compositions containing a stabilizer (Examples 31 to 41) showed a small difference in transmittance before and after irradiation at any measurement wavelength, as compared with Comparative Examples 4, 5, 6, 7, and 8 which did not contain a stabilizer, and were therefore confirmed to be excellent in stability.

[0169] Even when the compound having a sulfide group was Compound 9, the composition containing the stabilizer showed less change in color before and after irradiation, inhibited coloring, and was confirmed to have excellent stability, compared to the comparative example not containing a stabilizer.

[0170]

[0171]

[0172]

[0173]

Claims

1. A stabilizer for use with a compound having a sulfide group directly bonded to an aromatic ring or heterocyclic ring with a molecular weight of 1,000 or less, the stabilizer comprising at least one stabilizer A selected from phenolic compounds, aromatic amine compounds, sulfur-containing fatty acid compounds, phosphite ester compounds, phosphine compounds, carbamate compounds, and benzimidazole compounds.

2. The stabilizer according to claim 1, further comprising a stabilizer B which is a hindered amine compound.

3. The compound having a sulfide group has a carbon atom of any one skeleton selected from a benzotriazole skeleton, a benzophenone skeleton, a benzoate ester skeleton, and a triazine skeleton, and the carbon atom has a group represented by the following formula (i): (In the formula, R 1 represents a divalent hydrocarbon group in which a hydrogen atom may be substituted or a carbon atom may be interrupted, and R 2 represents a monovalent hydrocarbon group in which a hydrogen atom may be substituted or a carbon atom may be interrupted, and m represents an integer of 0 to 3.

4. The stabilizer according to claim 1, which is used in an organic material and / or inorganic material composition containing the compound having a sulfide group.

5. A composition comprising the stabilizer according to claim 1 and a compound having a sulfide group directly bonded to an aromatic ring or heterocyclic ring with a molecular weight of 1,000 or less.

6. The composition according to claim 5, wherein the stabilizer further comprises a stabilizer B which is a hindered amine compound.

7. An organic and / or inorganic material composition comprising the stabilizer according to claim 1, a compound having a sulfide group directly bonded to an aromatic ring or heterocyclic ring with a molecular weight of 1,000 or less, and an organic and / or inorganic material.

8. A method for improving the stability of a compound having a sulfide group, comprising adding the stabilizer according to claim 1 and a compound having a sulfide group directly bonded to an aromatic ring or heterocyclic ring with a molecular weight of 1,000 or less to an organic material and / or inorganic material composition, and allowing them to coexist in the composition.

9. The method according to claim 8, wherein the stabilizer further comprises a stabilizer B which is a hindered amine compound.

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