JP2013245269A - Method for producing stabilizer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stabilizer composition including a monoester and a diester of alkylmercapto carboxylic acid of bisphenol sulfide, which can maintain handling properties without precipitating solid matter even in a low-temperature environment.SOLUTION: A stabilizer composition contains a diester represented by general formula (1) (wherein, R, Rand Reach independently represents a hydrogen atom or the like, and Rand Reach independently represents optionally substituted 3-30C linear or branched alkyl) and a monoester. The content of the diester is more than 65 pts.mass and less than 80 pts.mass relative to 100 pts.mass in total of the diester and the monoester.

Description

  The present invention relates to a stabilizer composition for a synthetic resin, and particularly relates to a stabilizer composition that does not precipitate a solid even in a low temperature environment and has good handleability.

  So far, stabilizer compositions comprising monoesters of bisphenol sulfide alkyl mercaptocarboxylic acid and diesters thereof are polyvinyl chloride resin, polyethylene resin, polypropylene resin, polybutene resin, polybutylene terephthalate resin, polycarbonate resin, ABS. It is known to give an excellent stabilizing effect to various synthetic resins such as resin, nylon 6, nylon 66, ethylene-vinyl acetate copolymer, petroleum resin, coumarone resin (Patent Documents 1 to 4). ).

Japanese Patent Laid-Open No. 51-70192 Japanese Patent Laid-Open No. 52-154851 JP 54-083950 A JP-A-55-149338

  However, the stabilizer composition containing a monoester and a diester of alkyl mercaptocarboxylic acid of bisphenol sulfide is not particularly problematic in terms of storage stability under a normal temperature environment of about 25 ° C. In the case of long-term storage, there is a problem that the stabilizer composition becomes solid and handling becomes difficult, and improvement has been demanded. Patent Documents 1 to 4 describe the excellent stabilizing effect of such a stabilizer composition, but do not particularly mention the problem relating to the storage stability when the stabilizer composition is stored for a long period of time. No solution has been suggested.

  Accordingly, an object of the present invention is a stabilizer composition containing a monoester and a diester of an alkyl mercaptocarboxylic acid of bisphenol sulfide, which does not precipitate a solid even in a low temperature environment and can maintain the handleability. It is to provide a composition.

（式中、Ｒ^１、Ｒ^２及びＲ^３は、各々独立して、水素原子、炭素原子数１〜１８のアルキル基、炭素原子数３〜１８のシクロアルキル基、または、アルキル基、アルコキシ基、アルケニル基、アルケニルオキシ基またはヒドロキシ基で置換されていてもよい炭素原子数６〜３０のアリール基を表し、Ｒ^４およびＲ^５は各々独立に、アルコキシ基、アルケニル基、アルケニルオキシ基、ヒドロキシ基又はシアノ基で置換されていてもよい炭素原子数３〜３０の直鎖または分岐アルキル基を表す。）で表されるジエステル体、および、
下記一般式（２）、

（式中、Ｒ^１、Ｒ^２及びＲ^３は、各々独立して、水素原子、炭素原子数１〜１８のアルキル基、炭素原子数３〜１８のシクロアルキル基、又は、アルキル基、アルコキシ基、アルケニル基、アルケニルオキシ基またはヒドロキシ基で置換されていてもよい炭素原子数６〜３０のアリール基を表し、Ｒ^６は、アルコキシ基、アルケニル基、アルケニルオキシ基、ヒドロキシ基又はシアノ基で置換されていてもよい炭素原子数３〜３０の直鎖または分岐アルキル基を表す。）で表されるモノエステル体を含む安定剤組成物であって、
前記式（１）で表されるジエステル体と前記式（２）で表されるモノエステル体の合計１００質量部中、前記式（１）で表されるジエステル体の含有量が、６５質量部より多く、８０質量部未満であることを特徴とするものである。 That is, the stabilizer composition of the present invention has the following general formula (1),

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an alkyl group or an alkoxy group. Represents an aryl group having 6 to 30 carbon atoms which may be substituted with an alkenyl group, an alkenyloxy group or a hydroxy group, and R ⁴ and R ⁵ each independently represents an alkoxy group, an alkenyl group, an alkenyloxy group, a hydroxy group A diester body represented by a straight chain or branched alkyl group having 3 to 30 carbon atoms which may be substituted with a group or a cyano group, and
The following general formula (2),

Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an alkyl group or an alkoxy group. Represents an aryl group having 6 to 30 carbon atoms which may be substituted with an alkenyl group, alkenyloxy group or hydroxy group, and R ⁶ is substituted with an alkoxy group, alkenyl group, alkenyloxy group, hydroxy group or cyano group And a stabilizer composition comprising a monoester represented by a linear or branched alkyl group having 3 to 30 carbon atoms, which may be
In a total of 100 parts by mass of the diester represented by the formula (1) and the monoester represented by the formula (2), the content of the diester represented by the formula (1) is 65 parts by mass. More than 80 parts by mass.

  The stabilizer composition of the present invention preferably has a viscosity of 6,000 mPa · s or less. When using a pump to charge the stabilizer composition of the present invention into a synthetic resin or the like, a known pump such as a gear pump, a diaphragm pump, a rotary pump, a screw pump, a work pump, a sine pump, or a hose pump is used. However, if the viscosity of the stabilizer composition exceeds 6,000 mPa · s, a special pump may be required, or the stabilizer composition may adhere to the pump or the inner wall of the pipe and increase loss. Therefore, it is preferably 6,000 mPa · s or less. In order to reduce the viscosity of the stabilizer composition of the present invention to 6,000 mPa · s or less, the diester represented by the general formula (1) and the monoester represented by the general formula (2) It is necessary to adjust to a specific composition ratio.

In the stabilizer composition of the present invention, it is preferable that R ⁴ and R ⁵ in the general formula (1) and R ⁶ in the general formula (2) are all the same alkyl group.

  The resin composition of the present invention is characterized in that any one of the above stabilizer compositions is blended with a synthetic resin.

  The molded product of the present invention is formed by molding the above resin composition.

  The stabilizer composition of the present invention comprises an alkyl mercaptocarboxylic acid diester of bisphenol sulfide represented by the general formula (1) and an alkyl mercaptocarboxylic acid monoester of bisphenol sulfide represented by the general formula (2). Yes, in a total amount of 100 parts by mass of the compound of the formula (1) and the compound of the formula (2), the content of the compound represented by the general formula (1) is more than 65 parts by mass and less than 80 parts by mass. It is characterized by. The stabilizer composition of the present invention is a low-viscosity liquid with good handleability, and even when stored at a low temperature, for example, in an environment of 5 ° C., solid matter precipitation is suppressed. The viscosity is preferably 6,000 mPa · s or less. The viscosity is a viscosity at 25 ° C., and can be measured by, for example, a B-type viscometer.

  The stabilizer composition of the present invention preferably consists essentially of a diester represented by the above general formula (1) and a monoester represented by the above general formula (2). As long as the effects of the invention are not impaired, other components such as additives generally used in the resin as described below may be included. Even when other components are contained, the main component in the stabilizer composition of the present invention is the compound represented by the above general formula (1) and the compound represented by the general formula (2). Is preferably 1000 parts by mass or less with respect to 100 parts by mass in total of the diester represented by the general formula (1) and the monoester represented by the general formula (2).

As the optionally substituted linear or branched alkyl group having 3 to 30 carbon atoms represented by R ⁴ and R ⁵ in the general formula (1) and R ⁶ in the general formula (2), Propyl, isopropyl, butyl, isobutyl, t-butyl, s-butyl, amyl, isoamyl, neopentyl, hexyl, 2-ethylhexyl, isohexyl, heptyl, octyl, isooctyl, nonyl, decyl, isodecyl, lauryl, tetradecyl, hexadecyl, tridecyl, Examples include tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, tetracosyl, octacosyl and the like.

The alkyl group may be substituted with an alkenyl group, an alkenyloxy group, a hydroxy group, or a cyano group, and may be interrupted with an oxygen atom or a sulfur atom. These interruptions or substitutions may be combined. A compound having an alkyl group having less than 3 carbon atoms may bleed or fog on the surface of the molded product, which may impair the appearance of the molded product. If the alkyl group has more than 30 carbon atoms, the required stabilizing effect may not be obtained.
In the present invention, a stabilizer composition containing a compound in which R ⁴ , R ⁵ and R ⁶ are all the same alkyl group is preferably used because it has a relatively low viscosity and good thermal stability.

Examples of the alkyl group having 1 to 18 carbon atoms represented by R ¹ , R ² and R ³ in the general formulas (1) and (2) are the same as those described above for the alkyl group. It is done.

Examples of the cycloalkyl group having ³ to 18 carbon atoms represented by R ¹ , R ² and R ³ in the general formulas (1) and (2) include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and cycloheptyl. Group, cyclooctyl group, cyclononyl group, cyclodecyl group and the like, and a hydrogen atom in the cycloalkyl group may be substituted with an alkyl group, an alkenyl group, an alkenyloxy group, a hydroxy group, or a cyano group, The alkyl group may be interrupted by an oxygen atom or a sulfur atom. Examples include cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, 4-methylcyclohexyl and the like.

In the general formulas (1) and (2), a carbon atom which may be substituted with an alkyl group, an alkoxy group, an alkenyl group, an alkenyloxy group or a hydroxy group represented by R ¹ , R ² and R ³ Examples of the aryl group of 6 to 30 include phenyl group, methylphenyl group, butylphenyl group, octylphenyl group, 4-hydroxyphenyl group, 3,4,5-trimethoxyphenyl group, and 4-tert-butylphenyl. Group, biphenyl group, naphthyl group, methylnaphthyl group, anthracenyl group, phenanthryl group, benzyl group, phenylethyl group, 1-phenyl-1-methylethyl group and the like. In addition, a hydrogen atom in the aryl group may be substituted with an alkyl group, an alkenyl group, an alkenyloxy group, a hydroxy group, or a cyano group, and the alkyl group may be interrupted with an oxygen atom or a sulfur atom. Good

（式中、Ｒ^１〜Ｒ^５は各々一般式（１）と同様のものを表す。）
また、上記一般式（２）で表されるモノエステル体は、下記一般式（２’）で表されるものであることが好ましい。

（式中、Ｒ^１〜Ｒ^３およびＲ^６は各々一般式（２）と同様のものを表す。） The diester represented by the general formula (1) is preferably represented by the following general formula (1 ′).

(In the formula, R ^{1 to} R ⁵ each represents the same as in the general formula (1).)
Moreover, it is preferable that the monoester body represented by the said General formula (2) is what is represented by the following general formula (2 ').

(Wherein R ^{1 to} R ³ and R ⁶ each represents the same as in general formula (2))

  Specific examples of the structure of the compound represented by the general formula (1) include the following compounds. However, the present invention is not limited by the following compounds.

Specific examples of the compound represented by the general formula (2) include the following compounds. However, the present invention is not limited by the following compounds.

Synthetic resins stabilized by the stabilizer composition of the present invention include α-olefin polymers such as polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, polybutene-1, and poly-4-methylpentene. Or, polyolefins such as ethylene-vinyl acetate copolymer and ethylene-propylene copolymer and copolymers thereof, polyvinyl chloride, polyvinylidene chloride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer. Polymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-cyclohexyl Halogen-containing resin such as maleimide copolymer, petroleum resin, coumaro Copolymer of resin, polystyrene, polyvinyl acetate, acrylic resin, styrene and / or α-methylstyrene and other monomers (for example, maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.) For example, AS resin, ABS resin, MBS resin, heat-resistant ABS resin, etc.), polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyethylene terephthalate, polybutyl terephthalate, polytetramethyl terephthalate and other linear polyesters, polyphenylene oxide, Polyamides such as polycaprolactam and polyhexamethylene adipamide, polycarbonate, branched polycarbonate, polyacetal, polyphenylene sulfide, polyurethane, fiber Thermoplastic resins such as resins, and mixtures thereof, or can include phenolic resins, urea resins, melamine resins, epoxy resins, thermosetting resins such as unsaturated polyester resin. Further, it may be an elastomer such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, or may be included in the above resin.
In addition, the stabilizer composition of the present invention is also favorably used for synthetic resins for crosslinking produced by peroxides or radiation, and foamed resins such as foamed polystyrene.
Examples of the synthetic resin for crosslinking include polyethylene and copolymers such as ethylene-vinyl acetate, ethylene-ethyl acrylate, ethylene-propylene, and ethylene-propylene-butadiene.

  Moreover, as a crosslinking agent which can be used for a synthetic resin, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5- Dimethyl-2,5-di (t-butylperoxy) hexyne, 1,3-bis (t-butylperoxyisopropyl) benzene, t-butyl-hydroperoxide, cumene hydroperoxide, polysulfone azide, azidoformate, tetramethylisophthalyldi Examples thereof include tert-butyl bisperoxide, tetramethylisophthalyl dicumyl bisperoxide, alkanolamines such as diethanolamine and triethanolamine, hexamethylenediamine, and 4,4′-diaminodiphenylmethane.

  Of the above synthetic resins, polyolefin resins such as polyethylene, polypropylene, and ethylene-propylene copolymer resins are preferably used because of the excellent stabilization effect of the stabilizer composition of the present invention. That is, the stabilizer composition of the present invention is suitable as a stabilizer for polyolefin resins.

As described above, the stabilizer composition of the present invention may contain other components other than the compound represented by the general formula (1) and the compound represented by the general formula (2). Examples of other components include additives usually used for synthetic resins.
Moreover, you may add another component to the resin composition with which the stabilizer composition of this invention is mix | blended.
Examples of additives include phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, ultraviolet absorbers, hindered amine compounds, flame retardants, nucleating agents, fillers, lubricants, antistatic agents, Heavy metal deactivators, metal soaps, hydrotalcite, pigments, dyes, plasticizers and the like.

  The phenolic antioxidant may be the same as or different from that represented by the general formula (1). Examples of the phenolic antioxidant include 2,6-di-t-butyl-4-ethylphenol, 2-t-butyl-4,6-dimethylphenol, styrenated phenol, 2,2′-methylenebis ( 4-ethyl-6-tert-butylphenol), 2,2′-thiobis- (6-tert-butyl-4-methylphenol), 2,2′-thiodiethylenebis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate], 2-methyl-4,6-bis (octylsulfanylmethyl) phenol, 2,2'-isobutylidenebis (4,6-dimethylphenol), iso-octyl-3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis [3- (3,5-di-t-butyl- -Hydroxyphenyl) propionamide, 2,2'-oxamido-bis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2-ethylhexyl-3- (3 ', 5 '-Di-t-butyl-4'-hydroxyphenyl) propionate, 2,2'-ethylenebis (4,6-di-t-butylphenol), 3,5-bis (1,1-dimethylethyl) -4 -Ester of hydroxy-benzenepropanoic acid and C13-15 alkyl, 2,5-di-t-amylhydroquinone, hindered phenol polymer (trade name AO.OH998, manufactured by Adeka Palmalol), 2,2'-methylenebis [6- (1-Methylcyclohexyl) -p-cresol], 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-me Rubenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 6- [3- (3-t-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-t-butylbenz [d, f] [1,3,2] -dioxaphosphobin, Hexamethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis [monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate calcium salt, 5,7 -Bis (1,1-dimethylethyl) -3-hydroxy-2 (3H) -benzofuranone and the reaction product of o-xylene, 2,6-di-t-butyl-4- (4,6-bis (O Cutylthio) -1,3,5-triazin-2-ylamino) phenol, DL-a-tocophenol (vitamin E), 2,6-bis (α-methylbenzyl) -4-methylphenol, bis [3,3 -Bis- (4′-hydroxy-3′-t-butyl-phenyl) butanoic acid] glycol ester, 2,6-di-t-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol Stearyl (3,5-di-t-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-t-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-di-t- Butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5-di-t-butyl-4-hydroxyphenyl) propionate] 4,4′-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl-4-hydroxyphenoxy) -s-triazine, 2, 2′-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (2 , 6-di-t-butylphenol), 4,4′-butylidenebis (6-t-butyl-3-methylphenol), 2,2′-ethylidenebis (4,6-di-t-butylphenol), 1, 1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, bis [2-t-butyl-4-methyl-6- (2-hydroxy-3-t-butyl-5- Mechi Rubenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-t- Butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate ] Methane, 2-t-butyl-4-methyl-6- (2-acryloyloxy-3-t-butyl-5-methylbenzyl) phenol, 3,9-bis [2- 3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [ β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate] and phenolic antioxidants represented by the general formula (1) are mentioned, and tetrakis [methylene-3- ( 3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane is preferably used because it is relatively inexpensive and has good cost performance.

  Examples of the phosphorus antioxidant include triphenyl phosphite, diisooctyl phosphite, heptakis triphosphite, triisodecyl phosphite, diphenylisooctyl phosphite, diisooctyloctylphenyl phosphite, diphenyltridecyl Phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris (dipropylene glycol) phosphite, diisodecyl pentaerythritol diphosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, bis (tridecyl) ) Phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, diphenyldecyl phosphite, dinonylphenyl bis (nonyl fe) Phosphite, poly (dipropylene glycol) phenyl phosphite, tetraphenyldipropyl glycol diphosphite, trisnonylphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (2, 4-di-tert-butyl-5-methylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phos Phyto, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, distearyl pentaerythritol diphosphite, a mixture of distearyl pentaerythritol and calcium stearate, alkyl (C10) bisphenol A phosphite, Di (Tori Syl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-) 4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetraphenyl Tetra (tridecyl) pentaerythritol tetraphosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4 , 4'-n-Butylidenebis (2-t-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, tetrakis (2, 4-di-t-butylphenyl) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, (1-methyl-1-propanyl-3-ylidene) tris (2-1,1-dimethylethyl) -5-methyl-4,1-phenylene) hexatridecyl phosphite, 2,2′-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6-di-t-butylphenyl) -octadecyl phosphite, 2,2'-ethylidenebis 4,6-di-tert-butylphenyl) fluorophosphite, 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl) phosphite, tris (2-[(2,4,8, 10-tetrakis-t-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 3,9-bis (4-nonylphenoxy) -2, 4,8,10-tetraoxa-3,9-diphosphasspiro [5,5] undecane, 2,4,6-tri-tert-butylphenyl-2-butyl-2ethyl-1,3-propanediolphos Phyto, poly 4,4'-isopropylidenediphenol C12-15 alcohol phosphite, 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-t-butylphenol Sufaito, and the like.

  Examples of the thioether-based antioxidant include tetrakis [methylene-3- (laurylthio) propionate] methane, bis (methyl-4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-t-butyl. Phenyl) sulfide, ditridecyl-3,3′-thiodipropionate, dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipro Pionate, lauryl / stearyl thiodipropionate, 4,4'-thiobis (6-t-butyl-m-cresol), 2,2'-thiobis (6-t-butyl-p-cresol), distearyl- Disulfide is mentioned.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5 -Dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tertiary Corruptible -6-benzotriazolyl phenol), 2-
Polyethylene glycol ester of (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxyethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-octylphenyl] benzo Triazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl Benzotriazole, 2- [2-hydroxy-3-tertiary butyrate] -5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tertiary amyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3 -Tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyloxymethyl) phenyl] benzotriazole, 2- [2-hydroxy 2- (2-hydroxyphenyl) benzo such as -4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl] benzotriazole Triazoles; 2- (2-hydroxy-4 Methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2 -Hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (3-C12-13 mixed alkoxy- 2-hydroxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -4 , 6-Bis (4-methylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxy-3-allylphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3 , 5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-hexyloxyphenyl) -1,3,5-triazine and the like 2- (2-hydroxyphenyl) -4,6- Diaryl-1,3,5-triazines; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, octyl (3,5-ditert Tributyl-4-hydroxy) benzoate, dodecyl (3,5-ditert-butyl-4-hydroxy) benzoate, tetradecyl (3,5-ditert-butyl-4-hydroxy) benzoate, hexadecyl (3,5-di) Tert-butyl-4-hydroxy) benzoate, octadecyl (3,5-ditert-butyl-4-hydroxy) benzoate, behenyl (3 Benzoates such as 5-ditert-butyl-4-hydroxy) benzoate; substituted oxanilides such as 2-ethyl-2′-ethoxyoxanilide and 2-ethoxy-4′-dodecyloxanilide; ethyl-α- Cyanoacrylates such as cyano-β, β-diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various metal salts or metal chelates, particularly nickel and chromium salts, Or chelate etc. are mentioned.

Examples of the hindered amine compound include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6. -Tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2, 3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6) -Tetramethyl-4-piperidyl) -di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-pi Lysyl) .di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5 -Di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6- Bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6 -Tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl) -N- (2,2,6, -Tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N- Butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8-12-tetraazadodecane, 1,6,11 -Tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, 1,6,11 -Tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, bis {4- (1-octyloxy-2,2,6,6-tetramethyl And le) piperidyl} decanedionate, bis {4- (2,2,6,6-tetramethyl-1-undecyloxy) piperidyl) carbonate and the like.
Among these, a compound in which the one linked to the position 1 of piperidine is N-oxyalkyl or N-methyl is preferable.

  Examples of the flame retardant include aromatic phosphoric acid such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-xylenyl phosphate, and resorcinol bis (diphenyl phosphate). Phosphonates such as esters, divinyl phenylphosphonate, diallyl phenylphosphonate and phenylphosphonic acid (1-butenyl), phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phospha Phosphonic acid esters such as phenanthrene-10-oxide derivatives, phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicresyl phosphazene, melamine phosphate, melamine pyrophosphate, Melamine phosphate, melam polyphosphate, ammonium polyphosphate, phosphorus-containing vinylbenzyl compounds and phosphorus-based flame retardants such as red phosphorus, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, brominated bisphenol A type epoxy resin, bromine Phenol novolac epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclo Octane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated polystyrene and 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, tribromophenyl Reimido, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate, pentabromobenzyl acrylate, and include brominated flame retardants such as brominated styrene and the like.

  Examples of the nucleating agent include carboxylic acids such as sodium benzoate, 4-tert-butylbenzoic acid aluminum salt, sodium adipate and disodium bicyclo [2.2.1] heptane-2,3-dicarboxylate. Metal salts, sodium bis (4-tert-butylphenyl) phosphate, sodium-2,2′-methylenebis (4,6-ditert-butylphenyl) phosphate and lithium-2,2′-methylenebis (4,6-di) Phosphate metal salts such as tert-butylphenyl) phosphate, polyhydric alcohol derivatives such as dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, and bis (dimethylbenzylidene) sorbitol, N, N ′, N ″ -tris [2-methylcyclohexyl] -1,2,3-propanetricarboxamide (RIKACLEAR PC1), N, N ', N "-tricyclohexyl 1,3,5-benzenetricarboxamide, N, N'-dicyclohexyl-naphthalenedicarboxamide, 1,3 Amide compounds such as 5-tri (dimethylisopropoylamino) benzene.

  Examples of the filler include talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, Dolomite, mica, silica, alumina, potassium titanate whisker, wollastonite, fibrous magnesium oxysulfate and the like are preferable. Among these fillers, those having an average particle diameter (spherical or flat) or an average fiber diameter (needle or fibrous) are preferably 5 μm or less.

  The above-mentioned lubricant is added for the purpose of imparting lubricity to the surface of the molded body and enhancing the effect of preventing damage. Examples of the lubricant include unsaturated fatty acid amides such as oleic acid amide and erucic acid amide; saturated fatty acid amides such as behenic acid amide and stearic acid amide. These may be used alone or in combination of two or more.

  The antistatic agent is added for the purpose of reducing the chargeability of the molded product and preventing dust from adhering due to charging. Examples of the antistatic agent include cationic, anionic and nonionic. Preferred examples include polyoxyethylene alkylamines, polyoxyethylene alkylamides or their fatty acid esters, glycerin fatty acid esters, and the like.

  The range of the preferable usage-amount of the other additive used by this invention is a range from which the improvement of an addition effect is not seen from the quantity by which an effect is expressed. The amount of each additive used is 0.1 to 20 parts by mass of the plasticizer, 1 to 50 parts by mass of the filler, 0.001 to 1 part by mass of the surface treatment agent, relative to 100 parts by mass of the synthetic resin. 0.001 to 10 parts by mass of a phenolic antioxidant, 0.001 to 10 parts by mass of a phosphorus antioxidant, 0.001 to 10 parts by mass of a thioether antioxidant, and 0.001 to 5 parts by mass of an ultraviolet absorber. Part, hindered amine compound 0.01 to 1 part by mass, flame retardant 1 to 50 parts by mass, lubricant 0.03 to 2 parts by mass, antistatic agent 0.03 to 2 parts by mass, and nucleating agent 0. It is preferable that it is 01-10 mass parts. In addition, these additives may be used individually by 1 type, and may be used in combination of 2 or more types.

  The resin composition of the present invention is obtained by blending the stabilizer composition of the present invention with the above-described synthetic resin. The amount of the stabilizer composition of the present invention is preferably 0.01 to 5.0 parts by mass, more preferably 0.1 to 1.0 parts by mass with respect to 100 parts by mass of the synthetic resin.

  The molded product of the present invention is obtained by molding the resin composition of the present invention by a known molding method such as extrusion molding, injection molding, hollow molding, compression molding or the like. Uses and forms of the molded article of the present invention include automobile interior and exterior products, food containers, cosmetic and clothing containers, food bottles, beverage bottles, edible oil bottles, seasoning bottles and other bottles, food packaging materials, Examples include wrapping materials, packaging materials such as transportation packaging materials, protective films for electronic materials, sheets and films such as protective sheets for electrical appliances, fibers, daily goods, toys, and the like.

  Hereinafter, the present invention will be described more specifically with reference to reference examples, examples, and comparative examples. However, the present invention is not limited to the following examples.

[Examples 1 to 5, Comparative Examples 1 and 2]
As the diester represented by the general formula (1), in the general formula (1 ′), R ^{1 to} R ³ are hydrogen atoms, and R ⁴ and R ⁵ are each a substituent described in the table. As a compound and a monoester represented by the general formula (2), in the general formula (2 ′), R ^{1 to} R ³ are hydrogen atoms, and R ⁶ is a substituent described in the table. Each compound was added to each reagent glass bottle, stirred well, sealed, and placed in a 5 ° C. incubator. The following evaluation was performed on these samples.

[Reference Example 1]
About the sample of the comparative example 1 of Table 1, it left at normal temperature (25 degreeC), without using a 5 degreeC thermostat, and performed the following evaluation.

<Low temperature storage>
The state of the sample was visually observed every week. Evaluation was performed by the following method.
−: Liquid and solid matter is not observed.
A: A solid substance slightly precipitated.
B: A large solid was deposited, but more than half was liquid.
C: More than half precipitated as a solid.
D: The whole amount precipitated as a solid.

  The viscosity was measured under the conditions of (B-type viscometer / No. 4 router / 25 ° C./60 rpm) for the sample after 5 months.

<Handability>
The sample was put into a 100 g flask, the flask was inverted at 25 ° C. (room temperature), and the time until 97 g of the sample fell into a beaker serving as a tray was measured. The case where the time until 97 g dropped was within 5 minutes was evaluated as ◯, the case within 8 minutes after 5 minutes passed, and the case where more than 8 minutes passed were evaluated as x. These results are shown in Table 1.

  From Comparative Example 1, when the ratio of the compound represented by Formula (1) is 80 parts by mass or more with respect to 100 parts by mass of the total amount of the compounds represented by General Formula (1) and General (2), It was confirmed that the storage stability in a low temperature environment deteriorated and solid matter was generated after 2 months. Moreover, from the comparative example 2, the ratio of the compound represented by Formula (1) is 65 mass parts or less with respect to 100 mass parts of total amounts of the compounds represented by General Formula (1) and (2). It was confirmed that the viscosity became higher than 6,000 mPa · s. In addition, from the reference example 1, even if the ratio of the compound represented by Formula (1) exceeded 80 mass parts, when it preserve | saved at normal temperature, the solid substance did not generate | occur | produce.

  On the other hand, from Examples 1-5, the ratio of the compound represented by Formula (1) is 65 with respect to 100 mass parts of total amounts of the compound represented by General Formula (1) and (2). The stabilizer composition of the present invention that is in the range of more than 80 parts by weight and less than 80 parts by weight is excellent in handleability at a low viscosity of 6,000 mPa · s or less without generating solids even in a low temperature environment. It was confirmed that a liquid stabilizer could be obtained.

Claims (5)

The following general formula (1),

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an alkyl group or an alkoxy group. Represents an aryl group having 6 to 30 carbon atoms which may be substituted with an alkenyl group, an alkenyloxy group or a hydroxy group, and R ⁴ and R ⁵ each independently represents an alkoxy group, an alkenyl group, an alkenyloxy group, a hydroxy group A diester body represented by a straight chain or branched alkyl group having 3 to 30 carbon atoms which may be substituted with a group or a cyano group, and
The following general formula (2),

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an alkyl group or an alkoxy group. Represents an aryl group having 6 to 30 carbon atoms which may be substituted with an alkenyl group, alkenyloxy group or hydroxy group, and R ⁶ is substituted with an alkoxy group, alkenyl group, alkenyloxy group, hydroxy group or cyano group And a stabilizer composition comprising a monoester represented by a linear or branched alkyl group having 3 to 30 carbon atoms, which may be
In a total of 100 parts by mass of the diester represented by the formula (1) and the monoester represented by the formula (2), the content of the diester represented by the formula (1) is 65 parts by mass. More than and less than 80 mass parts stabilizer composition characterized by the above-mentioned.   The stabilizer composition according to claim 1, wherein the viscosity is 6,000 mPa · s or less. 3. The stabilizer composition according to claim 1, wherein R ⁴ and R ⁵ in the general formula (1) and R ⁶ in the general formula (2) are all the same alkyl group.   A resin composition comprising the stabilizer composition according to any one of claims 1 to 3 in a synthetic resin.   A molded product obtained by molding the resin composition according to claim 4.