JP5202883B2 - Emulsion for preventing yellowing - Google Patents

Description

  The present invention comprises one or more hindered amines containing at least one nonionic surfactant having an average molecular weight of 800 to 20000 as an emulsifier, having a solid content of 20 to 70% and an average particle diameter of 1 μm or less. The present invention relates to a light stabilizer and one or more ultraviolet absorbers; one or more hindered amine light stabilizers; or one or more ultraviolet absorbers for preventing yellowing.

Conventionally, in the fields of paper, fiber, plastic, etc., yellowing during long-term storage has long been a problem.
In the paper field, lignin is the main causative component. For example, Patent Document 1 describes a varnish containing an ultraviolet absorber and / or a hindered amine light stabilizer to delay yellowing of a lignin-rich cardboard sheet. Yes. In Patent Document 2, it is considered that yellowing occurs due to concentration of residual lignin to a specific part by drying in wet tissue made of bleached pulp sheet, and yellowing is effectively suppressed by containing polyethylene glycol.・ It is described that it is prevented. In Patent Document 3, in a wet tissue composed of bleached pulp sheet, a mixture of saccharide substances (disaccharides) derived from cellulose and hemicellulose remaining in the pulp is subjected to air oxidation and denatured to generate colored groups. It is estimated that yellowing occurs, and it is described that yellowing is prevented by containing sodium lactate or calcium chloride. Patent Document 4 discloses a method for producing a coated paper that is soft and calendered at a low nip, high temperature, and high speed, and is bulky and excellent in opacity but has little discoloration due to yellowing. In Patent Document 5, an environmentally friendly resin composition using paper is described as a fiber material for resin blending, and when water is applied to the resin composition or a molded product, the part is locally yellowed, It is described that this coloring component is derived from paper.

In the field of fibers and plastics, Patent Document 6 describes a polyamide fiber structure for preventing yellowing and a method for producing the same, and a terminal amino group is involved in yellowing of a polyamide-based fiber. It is described that treatment with an acid anhydride reduces terminal amino groups and prevents yellowing.
Patent Document 7 describes that yellowing is prevented by containing a benzotriazole ultraviolet absorber and a metal deactivator in the polyurethane composition and polyurethane elastic yarn. Patent Document 8 describes that a soft polyurethane foam contains one or more of an antioxidant, a hindered amine light stabilizer, and an ultraviolet absorber, so that it is difficult to yellow even with NOx gas.

However, in order to prevent yellowing, there is no patent document describing an emulsion for preventing yellowing in which a hindered amine light stabilizer, an ultraviolet absorber or the like is emulsified.
JP 2006-240734 A JP 2006-3002 A JP-A-9-70372 JP 2006-37257 A JP 2006-265348 A JP 2002-138367 A JP 2000-169700 A JP 2002-97245 A

  The object of the present invention is to use one or more hindered amine light stabilizers and one or more UV absorbers; one or more hindered amine light stabilizers used in the fields of paper, fibers, plastics, etc., especially in the paper field. Or an emulsion for preventing yellowing of one or more ultraviolet absorbers (hereinafter, also referred to as “one or more hindered amine light stabilizers and / or one or more ultraviolet absorbers”).

  In order to solve the above problems in the field of paper and the like, the present inventors can uniformly disperse the emulsion aqueous solution on paper if an emulsion of a hindered amine light stabilizer and / or an ultraviolet absorber is prepared. As a specific emulsifier, non-ionic surface activity with an average molecular weight of 800 to 20000, preferably ethylene oxide of distyrenized cresol, is considered to exhibit a yellowing prevention effect. By containing at least one selected from the group consisting of adduct type nonionic surfactants, pluronic type nonionic surfactants and polyoxyethylene higher alkyl ether type nonionic surfactants, A suitable emulsion of a hindered amine light stabilizer and / or UV absorber can be obtained, and It was found that Luchon has an effect of preventing yellowing, and the present invention was completed.

That is, the present invention
(1) One or more hindered amine light containing at least one nonionic surfactant having an average molecular weight of 800 to 20000 as an emulsifier, having a solid content of 20 to 70% and an average particle diameter of 1 μm or less. A stabilizer and one or more UV absorbers; one or more hindered amine light stabilizers; or an emulsion for preventing yellowing of one or more UV absorbers;
(2) One or more nonionic surfactants are distyrenated cresol ethylene oxide adduct type nonionic surfactants, pluronic type nonionic surfactants and polyoxyethylene higher alkyl ether type nonions An emulsion for preventing yellowing according to item (1), which is selected from the group consisting of surfactants,
(3) One or more hindered amine light stabilizers are bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine and Selected from the group consisting of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and one or more UV absorbers are 2- (2-hydroxy-5-t-butylphenyl) -2H- Benzotriazole, 2- (5-methyl-2-hydroxyphenyl) -2H-benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-ben Zotriazol, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5 Chloro-2H-benzotriazol, 2- (3,5-di-t-amyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-t-octylphenyl) -2H- From the group consisting of benzotriazole and C7-C9 branched and straight chain alkyl [3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxyphenyl] propionate The emulsion for preventing yellowing according to (1) or (2),
(4) One or more hindered amine light stabilizers are bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and 1- [2- [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine One or more UV absorbers selected from the group consisting of C7-C9 branched and straight chain alkyl [3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4 -Hydroxyphenyl] propionate, an emulsion for preventing yellowing according to (1) or (2),
(5) As an emulsifier, at least one polyoxyethylene higher alkyl ether type nonionic surfactant having a molecular weight of 800 to 2000 is contained, and at least one hindered amine light stabilizer is bis (1,2,2). , 6,6-pentamethyl-4-piperidyl) sebacate and one or more UV absorbers are C7-C9 branched and straight chain alkyl [3- (2H-benzotriazol-2-yl) -5- ( (1,1-dimethylethyl) -4-hydroxyphenyl] propionate, the emulsion for preventing yellowing according to item (1),
(6) The emulsion for preventing yellowing according to (5), wherein the emulsion is an emulsion of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate,
(7) As an emulsifier, one or more types of distyrenated cresol ethylene oxide adduct type nonionic surfactants having a molecular weight of 1000 to 6000 and one or more types of pluronic type nonionic surfactants having a molecular weight of 6000 to 20000 1- [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl containing a nonionic surfactant selected from the group consisting of one or more hindered amine light stabilizers Oxy] ethyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, one or more UV absorbers C7-C9 branched and straight chain alkyl [3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydro Shifeniru is a propionate, (1) above, wherein the yellowing-prevention emulsion,
(8) A paper base material containing 0.1 to 1.0% of the yellowing prevention emulsion according to (1) to (7).
(9) The paper base material according to item (8), wherein the paper base material is selected from the group consisting of medium quality paper, high quality paper, recycled paper, and coated paper.

The emulsion for preventing yellowing of the hindered amine light stabilizer and / or ultraviolet absorber of the present invention is excellent in the effect of preventing yellowing in the fields of paper, fibers, plastics, etc., particularly in the paper field, and is a medium quality paper. , Printed materials and packaging materials that use polypropylene resin, polyester resin, vinyl chloride resin as a film or sheet on a paper base such as high-quality paper, recycled paper, and coated paper, and a urethane adhesive layer It is excellent in preventing yellowing of cardboard materials and the like, and is particularly useful for preventing yellowing of printed displays such as books, posters used in the field, stickers and labels. Furthermore, since the emulsion for preventing yellowing of the present invention contains a hindered amine light stabilizer and / or an ultraviolet absorber, it can be used as an additive to various plastics.

  The hindered amine light stabilizer used in the present invention is not particularly limited as long as it is a hindered amine light stabilizer. For example, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2 , 2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate Preferably bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- [3- (3,5-di-t-butyl-4- Hydroxyph Nyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine or bis (2,2 , 6,6-tetramethyl-4-piperidyl) sebacate, particularly preferably bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate or 1- [2- [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2, 6,6-tetramethylpiperidine.

The ultraviolet absorber used in the present invention may be, for example, a benzotriazole type, a benzophenone type, a benzoate type, a cyanoacrylate type, or the like, and preferably a benzotriazole type.
Examples of the benzotriazole-based ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole and 2- (3-t-butyl-2-hydroxy-5-methylphenyl) -5. Chloro-2H-benzotriazol, 2- (3,5-di-t-pentyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H- Benzotriazol, 2- (5-methyl-2-hydroxyphenyl) -2H-benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazo- 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) ) -5-chloro-2H-benzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-tert-octyl) Phenyl) benzotriazole, C7-C9 branched and straight chain alkyl [3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxyphenyl] propionate, etc. And preferably 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) -2H-benzotriazole, 2- [2 -Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -2 -Benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di-t-amyl-2-hydroxy Phenyl) -2H-benzotriazole, 2- (2-hydroxy-5-t-octylphenyl) -2H-benzotriazole or C7-C9 branched and straight chain alkyl [3- (2H-benzotriazole-2 -Yl) -5- (1,1-dimethylethyl) -4-hydroxyphenyl] propionate, particularly preferably C7-C9 branched and straight chain alkyl [3- (2H-benzotriazole-2- Yl) -5- (1,1-dimethylethyl) -4-hydroxyphenyl] propionate.

  Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate, and 2-hydroxy-4-octyl. It may be oxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, etc., preferably 2-hydroxy-4-methoxybenzophenone or 2-hydroxy-4-octyloxybenzophenone And particularly preferred is 2-hydroxy-4-octyloxybenzophenone.

  The benzoate UV absorber may be, for example, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate.

The cyanoacrylate-based ultraviolet absorber can be, for example, 2′-ethylhexyl 2-cyano-3,3-diphenyl acrylate.
Said ultraviolet absorber can be used together mutually.

The nonionic surfactant (having an average molecular weight of 800 to 20000) used in the present invention is, for example, an ethylene oxide adduct type nonionic surfactant of styrenated phenol and / or styrenated cresol, or a pluronic type nonionic. Surfactants, polyoxyethylene higher alkyl ether type nonionic surfactants, and the like.
Nonionic surfactants of the ethylene oxide adduct type of styrenated phenol and / or styrenated cresol include mono, di, tri-styrenated phenol and / or ethylene oxide adduct of mono, di, tri-styrenated cresol. The nonionic surfactant of the ethylene oxide adduct type of styrenated phenol and / or styrenated cresol is preferably an ethylene oxide adduct of distyrenated phenol and / or distyrenized cresol, particularly preferably distyrenated. It is an ethylene oxide adduct of cresol. Further, the non-ionic surfactant of the ethylene oxide adduct type of distyrenated cresol is preferably a distyrenated m- or p-cresol and a mixture thereof with addition of ethylene oxide. If the body is a main component of 70% by weight or more, an ethylene oxide adduct of monostyrenated cresol and / or an ethylene oxide adduct of tristyrenated cresol may be mixed. The number of moles of ethylene oxide added to the distyrenated cresol is not particularly limited as long as the average molecular weight is within the range of the present invention, but is preferably 10 to 150 moles, particularly preferably 20 moles to 100 moles, The average molecular weight is 1000 to 6000.

  The pluronic-type nonionic surfactant is a block polymer of ethylene oxide, propylene oxide, and ethylene oxide, and is not particularly limited as long as the average molecular weight is within the range of the present invention. Preferably, the average chain length of the polyethyleneoxy group is 25 To 250, an average chain length of polypropyleneoxy group of 10 to 100 and an average chain length of polyethyleneoxy group of 25 to 250, particularly preferably an average chain length of polyethyleneoxy group of 60 to 200 and an average chain length of polypropyleneoxy group. The average chain length of polyethylene oxy groups is 20 to 70, and the average molecular weight is 6000 to 20000.

  The polyoxyethylene higher alkyl ether type nonionic surfactant is one in which ethylene oxide is added to one or more higher alcohols having 8 to 18 carbon atoms, and the average molecular weight of ethylene oxide addition moles is within the scope of the present invention. Although there is no particular limitation, it is preferably 15 to 100, and particularly preferably 15 to 50. The higher alcohol ethylene oxide adduct is preferably an ethylene oxide adduct of one or more higher alcohols having 10 to 18 carbon atoms, particularly preferably an ethylene oxide adduct of a mixture of decyl alcohol and cetyl alcohol. Is 800 to 2000.

  The method for producing the emulsion varies depending on the kind of the hindered amine light stabilizer and / or the kind of the UV absorber, but is achieved by including one or more nonionic surfactants having an average molecular weight of 800 to 20000 as an emulsifier. Is done. The emulsifier is not particularly limited, but is preferably a commercially available TK combination (manufactured by Tokushu Kika Kogyo Co., Ltd.) or Ultra Turrax T25 (18N) (manufactured by IKA). When one or both of the hindered amine light stabilizer and / or the ultraviolet absorber is liquid, a nonionic surfactant is added, stirred using an emulsifier, and mixed uniformly. Next, water is added and phase inversion emulsification is performed to obtain the desired emulsion. When one or both of the hindered amine light stabilizer and / or the ultraviolet absorber is powder or crystal, it is homogenized using a solvent. A nonionic surfactant and water are added and stirred with an emulsifier to obtain an emulsion. The emulsion is desolvated and the solid content is adjusted with water to obtain the target emulsion. The solvent used is not particularly limited, but is preferably a solvent that can be easily removed, for example, aromatic hydrocarbons such as benzene, toluene, and xylene, alicyclic hydrocarbons such as cyclohexane, hexane, Aliphatic hydrocarbons such as octane, cyclic ethers such as tetrahydrofuran and dioxane, alcohols such as methanol, ethanol and isopropanol, glymes such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, ketones such as acetone and methyl ethyl ketone, ethyl acetate, etc. And nitriles such as acetonitrile, preferably aromatic hydrocarbons such as benzene, toluene and xylene. The solid content depends on the amount of water to be added, but is usually 20 to 70% solid content, and preferably 25 to 70%. The particle diameter is related to the stirring rotation speed of the emulsifier, and there is no particular limitation as long as the rotation speed can produce an emulsion having an average particle diameter of 1 μm or less (preferably an emulsion having a particle diameter of 0.34 μm to 0.75 μm). , Usually 500 to 20000 rpm, preferably 1000 to 18000 rpm.

  In producing an appropriate emulsion, the combination of the hindered amine light stabilizer and / or the UV absorber and the nonionic surfactant as an emulsifier is not particularly limited, but preferably the hindered amine light stabilizer is bismuth. (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate with UV absorber C7-C9 branched and linear alkyl [3- (2H-benzotriazol-2-yl) -5 -(1,1-dimethylethyl) -4-hydroxyphenyl] propionate (trade name: TINUVIN (registered trademark) 384-2, manufactured by Ciba Specialty Chemicals Co., Ltd.), the molecular weight is 800 to 2000 as an emulsifier. An emulsion is produced by phase inversion emulsification using a polyoxyethylene higher alkyl ether type nonionic surfactant. It is, particularly preferably, an average molecular weight of ethylene oxide adduct of a mixture of decyl alcohol and cetyl alcohol with nonionic surfactant 800 to 2000, by phase inversion emulsification, the emulsion is produced.

Further, the hindered amine light stabilizer is 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di- t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, the UV absorber is a C7-C9 branched and straight chain alkyl [3- (2H-benzotriazole- 2-yl) -5- (1,1-dimethylethyl) -4-hydroxyphenyl] propionate (trade name: TINUVIN (registered trademark) 384-2, manufactured by Ciba Specialty Chemicals Co., Ltd.) As an emulsifier, a combination of a distyrenized cresol ethylene oxide adduct type nonionic surfactant and a pluronic type nonionic surfactant is used. An emulsion is produced, and particularly preferably, an ethylene oxide adduct type nonionic surfactant having a molecular weight of 1000 to 6000 and a pluronic type nonionic surfactant having a molecular weight of 6000 to 20000 are used. An emulsion is produced.

  The emulsion thus obtained can be used in a wide range of fields such as a paper field, a fiber field, a plastic field, and a composite field thereof, and the paper field is particularly preferable.

When the emulsion of the present invention is added to the paper field, for example, medium base paper, high quality base paper, recycled paper, coated paper, etc., it may contain one or more fluorescent whitening agents, and its content (weight) is For example, it is 0.05 to 0.5% by weight, preferably 0.1 to 0.3% by weight, and particularly preferably, based on the weight of clay / calcium carbonate in the coating liquid. 0.1% by weight. The surface coating may contain calcium carbonate and / or clay, in particular kaolin, but usually the calcium carbonate / clay ratio is 30 to 80% by weight / 70 to 20% by weight, preferably calcium carbonate / The proportion of kaolin clay is 40-60% by weight / 60-40% by weight. The surface coating may also contain a binder, in particular starch, to improve its binding strength. The starch may be, for example, oxidized starch, hydroxyethyl etherified starch (HES) or the like, and is preferably hydroxyethyl etherified starch (HES). The starch content is usually 1 to 15% by weight, preferably 3 to 7% by weight, based on the weight of clay / calcium carbonate. As the surface coating agent, polyvinyl alcohol (PVA) or latex (Latex) can be blended. The blending amount of polyvinyl alcohol is usually 0.5 to 4% by weight, preferably 1 to 2% by weight, based on the weight of clay and calcium carbonate, and the blending amount of latex is the weight of clay and calcium carbonate. On the other hand, it is usually 5 to 20% by weight, preferably 8 to 15% by weight.
The emulsion of the present invention is preferably applied to paper before surface coating or after mixing with a surface coating agent. The added amount of the emulsion (in terms of solid content) is usually 0.05 to 4% by weight, preferably 0.1 to 2% by weight, more preferably, based on the weight of the clay / calcium carbonate. 0.1 to 1% by weight.

  When using a polypropylene resin, polyester resin, or vinyl chloride resin as a film or sheet on a paper substrate, or adding it to composite materials such as printed materials, packaging materials, and cardboard materials with a urethane adhesive layer Preferably, the emulsion of the present invention is added to the paper base material in advance by the addition method described above in the paper field and coated.

  In the fields of magazines, gravure, etc., thick paper, bulky, high opacity, and high-grade glossy paper use bulky coated paper. It is manufactured by applying a coating liquid containing a pigment such as calcium carbonate and an adhesive to a base paper using a roll coating device or a blade coating device, then drying, and then calendering the coated surface. ing. The adhesive of the coating liquid consists of starch, styrene, butadiene, acrylonitrile, methyl methacrylate, etc. In order to obtain an effective yellowing prevention effect, the emulsion of the present invention (in terms of solid content) is converted into clay / carbonic acid. Preferably, 0.05 to 4% by weight is added, more preferably 0.1 to 2% by weight, and particularly preferably 0.1 to 1% by weight, based on the weight of calcium.

  The emulsion of the present invention can be obtained by using polypropylene-based resin, polyester-based resin, vinyl chloride-based resin as a film or sheet on a paper substrate such as medium-quality paper, high-quality paper, recycled paper, coated paper, and glossy paper, or urethane. This is useful for preventing yellowing of printed matter display bodies and packaging materials provided with an adhesive layer, particularly printed matter display bodies such as books, posters, stickers and labels used outdoors.

  In fields other than paper, the emulsion of the present invention can be added to polyester, polyamide, polyurethane, biodegradable plastic, acrylic resin, etc. at the time of molding, but is preferably a resin produced by aqueous emulsion polymerization or the like. The emulsion of the present invention is added during the emulsion polymerization. The addition amount (in terms of solid content) of the emulsion of the present invention is usually 0.05 to 4% by weight, preferably 0.1 to 2% by weight, based on the total weight of the monomers.

  The paint can be classified into a paint using an organic solvent and a water-based paint. In particular, the emulsion of the present invention can be added to the water-based paint. The addition amount (in terms of solid content) of the emulsion of the present invention is usually 0.05 to 4% by weight, preferably 0.1 to 2% by weight, relative to the components other than the solvent.

  The emulsions of the present invention can be added to inks, dyes, particularly water-based inks and dyes. The addition amount (in terms of solid content) of the emulsion of the present invention is usually 0.05 to 4% by weight, preferably 0.1 to 2% by weight, relative to the components other than the solvent.

  In addition, the emulsion of the present invention can be used in combination with a processing agent such as a nucleating agent, a plasticizer, a filler, a reinforcing agent, an antistatic agent, a lubricant, an antioxidant, an antifungal agent, or a bactericidal agent, if necessary. .

EXAMPLES The present invention will be specifically described below with reference to examples, reference examples, comparative examples, and test examples of the present invention, but the present invention is not limited to these examples.

Example 1
1- [2- [3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Emulsion of propionyloxy] -2,2,6,6-tetramethylpiperidine 1- [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine 50 g and toluene 50 g were heated to 60 ° C. A homogeneous solution was obtained. On the other hand, ethylene oxide adduct of distyrenated cresol (average chain length of polyoxyethylene group 35, average molecular weight 1870, HLB 16.6) and ethylene oxide-propylene oxide-ethylene oxide block copolymer (pluronic type, average of polyoxyethylene group) 94 g of ion-exchanged water was added to 1 g of chain length 175, polyoxypropylene group average chain length 68, polyoxyethylene group average chain length 175, average molecular weight 19000, HLB16) to obtain a homogenized aqueous emulsifier solution. The uniform solution of the light stabilizer and the aqueous emulsifier solution were mixed, and stirred with Ultra Turrax T25 (18N) (manufactured by IKA) at 18000 rpm for 10 minutes to obtain a toluene-containing emulsion. This emulsion was detoluated and the solid content was adjusted with ion-exchanged water to obtain 224 g of the desired emulsion (solid content 25%, average particle size 0.75 μm).

Example 2
1- [2- [3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionyloxy] -2,2,6,6-tetramethylpiperidine and C7-C9 branched and straight chain alkyl [3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) ) -4-Hydroxyphenyl] propionate (trade name: TINUVIN (registered trademark) 384-2, manufactured by Ciba Specialty Chemicals Co., Ltd.) (weight ratio 3: 1) 1- [2- [3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2 , 2,6,6-tetramethylpiperidine 45 g and C7-C9 branched and straight chain alkyl [3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy Phenyl] propionate (trade name: TINUVIN (registered trademark) 384-2, Ciba Specialty Chemicals Co., Ltd.) 15 g and toluene 35 g are heated to 60 ° C. to obtain a uniform solution of a light stabilizer and an ultraviolet absorber. It was. On the other hand, ethylene oxide adduct of distyrenated cresol (average chain length of polyoxyethylene group 61, average molecular weight 3010, HLB17.9) and ethylene oxide-propylene oxide-ethylene oxide block copolymer (pluronic type, average of polyoxyethylene group) 88 g of ion-exchanged water was added to 1.8 g of chain length 175, polyoxypropylene group average chain length 68, polyoxyethylene group average chain length 175, average molecular weight 19000, HLB16) to obtain a homogenized aqueous emulsifier solution. A uniform solution of a light stabilizer and an ultraviolet absorber and an aqueous emulsifier solution were mixed and stirred with Ultra Turrax T25 (18N) (manufactured by IKA) at 18000 rpm for 10 minutes to obtain a toluene-containing emulsion. This emulsion was converted into toluene and the solid content was adjusted with ion-exchanged water to obtain 283 g of the desired emulsion (solid content 25%, average particle size 0.34 μm).

Example 3
1- [2- [3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionyloxy] -2,2,6,6-tetramethylpiperidine and C7-C9 branched and straight chain alkyl [3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) ) -4-Hydroxyphenyl] propionate (trade name: TINUVIN (registered trademark) 384-2, manufactured by Ciba Specialty Chemicals Co., Ltd.) (weight ratio 1: 1) 1- [2- [3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2 , 2,6,6-tetramethylpiperidine 30 g with C7-C9 branched and straight chain alkyl [3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy Phenyl] propionate (trade name: TINUVIN (registered trademark) 384-2, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 20 g of toluene are heated to 60 ° C. to obtain a uniform solution of a light stabilizer and an ultraviolet absorber. It was. On the other hand, ethylene oxide adduct of distyrenated cresol (average chain length 61 of polyoxyethylene group, average molecular weight 3010, HLB17.9) 4.5 g, ethylene oxide adduct of distyrenated cresol (average chain length 123 of polyoxyethylene group, Average molecular weight 5730, 4.5 g HLB 18.9) and ethylene oxide-propylene oxide-ethylene oxide block copolymer (pluronic type, polyoxyethylene group average chain length 175, polyoxypropylene group average chain length 68, polyoxyethylene group The average chain length 175, the average molecular weight 19000, HLB16) was added to 70 g of ion exchange water to obtain a homogenized aqueous emulsifier solution. A uniform solution of a light stabilizer and an ultraviolet absorber and an aqueous emulsifier solution were mixed and stirred with Ultra Turrax T25 (18N) (manufactured by IKA) at 18000 rpm for 10 minutes to obtain a toluene-containing emulsion. This emulsion was converted into toluene and the solid content was adjusted with ion-exchanged water to obtain 283 g of the desired emulsion (solid content 25%, average particle size 0.36 μm).

Reference example 4
Emulsions of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate TK (1, 2, 2, 6, 6-pentamethyl) was added to the TK combimix emulsifier (manufactured by Special Mechanized Industries Co., Ltd.) -4-piperidyl) sebacate 2200 g and polyoxyethylene decyl / cetyl ether (polyoxyethylene group average chain length 13.4, average molecular weight 870, HLB 13.6) were charged and stirred at an anchor blade speed of 150 rpm for 5 minutes. And mixed uniformly. Stirring was stopped, 330 g of ion-exchanged water was added to the emulsifier, the mixture was stirred for 5 minutes at an anchor blade rotation speed of 150 rpm, and then stirred for 10 minutes under the conditions of an anchor blade rotation speed of 150 rpm and a disper blade rotation speed of 5000 rpm. Was done. After phase inversion emulsification, the rotation speed is lowered to 100 rpm for the anchor blade and 1000 rpm for the disperse blade, and 973 g of ion-exchanged water is gradually added to adjust the solid content, and the target emulsion (solid content 65%, average particle) 3723 g) was obtained.

Reference Example 5
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and C7-C9 branched and straight chain alkyl [3- (2H-benzotriazol-2-yl) -5- (1,1 -Dimethylethyl) -4-hydroxyphenyl] propionate (trade name: TINUVIN (registered trademark) 384-2, manufactured by Ciba Specialty Chemicals Co., Ltd.) (weight ratio 3: 1) TK Combimix emulsifier (special Manufactured by Kika Kogyo Co., Ltd.) and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate 120 g, C7-C9 branched chain and linear alkyl [3- (2H-benzotriazole-2 -Yl) -5- (1,1-dimethylethyl) -4-hydroxyphenyl] propionate (trade name: TINUVIN® 384-2, Ciba Sustain) 40 g of Peachty Chemicals Co., Ltd.) and 16 g of polyoxyethylene decyl / cetyl ether (polyoxyethylene group average chain length of 13.4, average molecular weight of 870, HLB 13.6) were charged, and the speed of the disperse blade was 3 at 1000 rpm. Stir for minutes and mix evenly. Stirring was stopped, 24 g of ion-exchanged water was added to the emulsifier, and the mixture was stirred at 3000 rpm for 10 minutes to perform phase inversion emulsification. After phase inversion emulsification, the rotational speed of the disperser blade is reduced to 1000 rpm, 70 g of ion-exchanged water is gradually added to adjust the solid content, and the target emulsion (solid content 69.2%, average particle size 0.37 μm) 230 g was obtained.

Reference Example 6
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and C7-C9 branched and straight chain alkyl [3- (2H-benzotriazol-2-yl) -5- (1,1 -Dimethylethyl) -4-hydroxyphenyl] propionate (trade name: TINUVIN (registered trademark) 384-2, manufactured by Ciba Specialty Chemicals Co., Ltd.) (weight ratio 1: 1) TK Combimix emulsifier (special 80 g of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, C7-C9 branched chain and linear alkyl [3- (2H-benzotriazole-2 -Yl) -5- (1,1-dimethylethyl) -4-hydroxyphenyl] propionate (trade name: TINUVIN (registered trademark) 384-2, Ciba spe 80 g of Charty Chemicals Co., Ltd.) and 16 g of polyoxyethylene decyl / cetyl ether (polyoxyethylene group average chain length 13.4, average molecular weight 870, HLB 13.6) were charged, and the number of revolutions of the disperse blade was 3 at 1000 rpm. Stir for minutes and mix evenly. Stirring was stopped, 24 g of ion-exchanged water was added to the emulsifier, and the mixture was stirred at 3000 rpm for 10 minutes to perform phase inversion emulsification. After phase inversion emulsification, the rotational speed of the disperser blade is reduced to 1000 rpm, and 70 g of ion-exchanged water is gradually added to adjust the solid content. The target emulsion (solid content 68.3%, average particle size 0.42 μm) 270 g was obtained.

Test example 1
0.1 part by weight of the emulsion obtained in Example 1 and Reference Example 4 and 1.0 part of polyvinyl alcohol (PVA) as a blending material are added to a base mixture of 50 parts kaolin and 50 parts calcium carbonate, and 0.1 part A coating solution to which a fluorescent dye is added is prepared, and hand coating is performed on the surface of the medium base paper and the high quality base paper at a coating amount of 12.0 to 12.7 g / m ² with a winding Mayer bar (note that The emulsion obtained in Example 1 was hand-coated only on the surface of a high-quality base paper), and a test sample paper was prepared. Only a non-coated medium base paper and a high quality base paper are used as blanks, and no emulsion is added to a medium base paper or a high quality base paper as a comparative example. And produced as a sample paper for comparison.
Using these blanks, test and comparative sample papers as a light resistance tester, XENON WEATHER O-METER (Ci-65) (manufactured by Atlas), temperature: Black Panel Temperature 63 ° C., 45 ° C. in the bath, humidity: 50%, irradiation intensity: 0.39 W / m ² (340 nm), Outer filter: irradiated with borosilicate for 10 hours. Evaluation was performed using a spectrocolorimeter: CM-3700d (manufactured by Minolta Co., Ltd.).

Test example 2
0.1 part by weight of the emulsion obtained in Example 1 and Reference Example 4 was added to a base mixture of 50 parts kaolin and 50 parts calcium carbonate. 0.1 parts fluorescent dye, 4.0 parts hydroxyethyl etherified starch (HES), 11.0 parts latex (Latex: SBR latex), 0.5 parts wax (calcium stearate), The mixture was prepared so as to be uniform, and a coating solution was prepared. This coating solution was hand-coated with a wound Mayer bar on the surface of the high-quality base paper so as to be 13.0 to 16.8 g / m ² to prepare a sample paper for Latex blending test. Similarly, a comparative sample without an emulsion was prepared as a comparative example. Using these sample papers as in Test Example 1 as a light resistance tester, XENON WEATHER O-METER (Ci-65) (manufactured by Atlas Co., Ltd.), temperature: Black Panel Temperature 63 ° C., 45 ° C. in the tank, humidity: 50 %, Irradiation intensity: 0.39 W / m ² (340 nm), Out filter: irradiated with borosilicate for 10 hours. Evaluation was performed using a spectrocolorimeter: CM-3700d (manufactured by Minolta Co., Ltd.).

Test example 3
1.0 and 0.5 parts by weight of the emulsions obtained in Example 2 and Reference Example 6 , respectively, were added to a base mixture of 50 parts kaolin and 50 parts calcium carbonate. Furthermore, 0.1 part of fluorescent dye is added in terms of base mixture, 4.0 parts of hydroxyethyl etherified starch (HES), 11.0 parts of latex (Latex: SBR latex), 0.5 parts of wax ( (Calcium stearate) was mixed and prepared so as to be uniform to prepare a coating solution. Similarly, the surface of the high-quality base paper was coated by hand with a wound Mayer bar at a coating amount of 15.2 to 16.2 g / m ² to prepare a test sample paper. Similarly, a comparative sample without an emulsion was prepared as a comparative example. Using XENON WEATHER O-METER (Ci-65) (manufactured by Atlas Co., Ltd.) as a light resistance tester for the test sample paper, temperature: Black Panel Temperature 63 ° C., 45 ° C. in the tank, humidity: 50%, irradiation intensity: 0 .39 W / m ² (340 nm), Out filter: irradiated with a soda ram for 10 hours. Evaluation was performed using a spectrocolorimeter: CM-3700d (manufactured by Minolta Co., Ltd.).

塗工液は水を加えて固形分濃度が５５％になるように調製した。塗工原紙は２５ｃｍ幅Ｘ６０ｃｍ長さの上質紙（８３ｇ／ｍ^２）又は中質紙（４４ｇ／ｍ^２）を使用した。耐光性試験は２０ｍｍ幅Ｘ４０ｍｍ長さのサンプル紙を使用した。
また、「部」は、重量部を示す。 Table 1 shows the composition of the coating liquids of Comparative Examples and Test Examples.

The coating solution was prepared by adding water to a solid content concentration of 55%. As the coating base paper, a high-quality paper (83 g / m ² ) or a medium-quality paper (44 g / m ² ) having a width of 25 cm × 60 cm was used. In the light resistance test, a sample paper having a width of 20 mm and a length of 40 mm was used.
“Parts” indicates parts by weight.

Light Resistance Test Evaluation Table 2 shows the color difference (ΔE *) and chromaticity (Δb *) after 10 hours obtained in Test Example 1, Test Example 2, and Test Example 3. As shown in Table 2, the emulsions of the examples clearly showed an excellent yellowing prevention effect in color difference (ΔE *) and chromaticity (Δb *).

  The hindered amine light stabilizer and / or UV absorber emulsion for preventing yellowing of the present invention is excellent in the effect of preventing yellowing in the fields of paper, fibers, plastics, etc., especially in the paper field. It can be used as an anti-yellowing agent for plastics.

Claims (5)

It contains a nonionic surfactant that is a combination of an ethylene oxide adduct type nonionic surfactant of distyrenized cresol having an average molecular weight of 1000 to 6000 and a pluronic type nonionic surfactant having an average molecular weight of 6000 to 20000. , Ri solids 20 to 70% der, average particle is size 1μm or less, one or more hindered amine light stabilizer and one or more UV absorbers; one or more hindered amine light stabilizers; or one An emulsion for preventing yellowing of a paper base material of the above ultraviolet absorber, wherein one or more hindered amine light stabilizers are bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1 -[2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3 -Di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine and bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate And one or more UV absorbers are 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) -2H-benzotriazole 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -2H -Benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di-t-amyl-2 Hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole, and C7-C9 branched and straight chain alkyl [3- (2H-benzotriazole -2-yl) -5- (1,1-dimethylethyl) -4-hydroxyphenyl] propionate, an emulsion for preventing yellowing . The emulsion for preventing yellowing according to claim 1, wherein the average particle size is 0.34 to 1 µm. One or more hindered amine light stabilizers are 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine and one or more UV absorbers are C 7 -C 9 branched and straight chain alkyl [3 - (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxyphenyl] Ru propionate der claim 1 or 2 yellowing preventing emulsion according. The paper base material which coated the coating liquid which added the emulsion for yellowing prevention of any one of Claims 1-3. The paper substrate according to claim 4 , wherein the paper substrate is selected from the group consisting of medium quality paper, high quality paper, recycled paper and coated paper.