JP2005120137A - Polymer-bound ultraviolet absorber, ultraviolet absorber composition, ultraviolet screening composition, method for producing the same and processed article using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ultraviolet absorber producing a processed article having high transparency and an excellent ultraviolet screening ability without deteriorating moldability of a synthetic resin and performances of a coating material without causing bleed of the ultraviolet absorber, an ultraviolet absorber composition and an ultraviolet screening composition comprising the same compounded in a medium. <P>SOLUTION: The polymer-bound ultraviolet absorber is characterized in that the ultraviolet absorber obtained by condensing the ultraviolet absorber having reactive groups each mutually carrying out a condensation reaction with the reactive groups of the polymer is bound to the polymer chain. The ultraviolet screening composition is characterized in that the ultraviolet absorber composition composed of the ultraviolet absorber and an ultraviolet absorbing fine particulate white inorganic pigment and a medium are compounded with at least the ultraviolet absorber composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is a novel ultraviolet absorber, an ultraviolet absorber composition containing the same, and a high transparency obtained by blending this composition in a medium such as a polymer, excellent bleeding resistance, and excellent ultraviolet shielding effect. Ultraviolet shielding composition for providing processed article, processed article using the same, and more particularly, a polymer-bound ultraviolet absorbent in which an ultraviolet absorbent is bound to a polymer chain, and an ultraviolet absorbent composition comprising the fine-particle white inorganic pigment The present invention relates to an ultraviolet shielding composition obtained by blending the composition with a medium such as a polymer, and a processed article using the composition.

  Polymers such as synthetic resins cause embrittlement due to light exposure by sunlight, especially ultraviolet rays, etc. when the molded product is used or stored for a long period of time, resulting in reduced elasticity, reduced tensile strength, and generation of cracks. There are problems such as deterioration of mechanical properties such as deterioration of electrical properties, coloring, and the like. Similarly, in products in the field of coating materials using coating agents, paints, offset inks, gravure inks, printing agents, etc., in which a polymer is a film-forming component or binder, coating film gloss reduction, cracking, blistering, pigments Due to discoloration, discoloration, etc., or inappropriate selection of packaging materials, the contents may cause quality deterioration due to ultraviolet rays.

  In order to improve such problems, when molding a polymer, the polymer has conventionally been an ultraviolet absorber, particularly a benzotriazole ultraviolet absorber, a triazine ultraviolet absorber, or a salicylate ultraviolet absorber. In addition, benzophenone ultraviolet absorbers or inorganic white inorganic pigments such as fine particle titanium oxide and fine particle zinc oxide are blended and used. Usually, ultraviolet absorbers are used alone or in combination of two or more, or in combination with antioxidants, light stabilizers such as hindered amines, etc., and further antistatic agents for antistatic purposes. Has also been used.

  However, since these organic ultraviolet absorbers are generally low molecular weight compounds, various disadvantages are caused when they are used. For example, a compound having a relatively low boiling point (melting point) or a sublimable compound causes sublimation, volatilization, etc. during heat processing such as molding or heat curing, or during storage or use in a heated state. Or may be extracted from the synthetic resin or coating film by contact with warm water, acidic, alkaline aqueous solution, alcohol, oil or other organic solvent, etc. There was a case that could not be sustained.

In addition, when UV absorbers are used in combination with synthetic resins, if the compatibility with synthetic resins is poor, the surface of molded products and painted surfaces will bleed (blooming phenomenon) during long-term use. In addition to causing a decrease in the surface, problems such as stickiness on the surface, deterioration in adhesion and printability, and contamination of other articles may occur. In addition, adding a large amount of UV absorber to a synthetic resin beyond its solubility and compatibility limits will cause phase separation and reduce the transparency and mechanical strength of the synthetic resin. There was a limit to the amount, and improvements were required. In addition, low molecular weight ultraviolet absorbers may be irritating to the skin and mucous membranes depending on the compound, and in the case of powders, there are those that require attention in terms of safety and hygiene such as generation of dust.
In order to solve these problems, UV absorbers are proposed in which lactones are subjected to ring-opening polymerization using a specific UV-absorbing benzotriazole-based compound, and the above compound is bonded to the end of the resulting polyester chain. However, the above compound is only the terminal of the molecular chain, and it is necessary to increase the amount used (Patent Document 1).

  On the other hand, when mixed with synthetic resin, fine particle white inorganic pigment, such as fine particle titanium oxide or fine particle zinc oxide, as an inorganic ultraviolet absorbing pigment, it does not bleed on the surface of the molded product or painted surface, but absorbs ultraviolet light. In order to produce an effect, it is necessary to mix with a synthetic resin in a large amount, and the transparency of the synthetic resin is lowered.

Japanese Patent Laid-Open No. 10-265556

The object of the present invention is to provide a novel ultraviolet absorber, an ultraviolet absorber composition, and a composition that is free from the problems of the prior art described above, and when blended with a medium such as a polymer, the transparency is high and the bleeding resistance is high. It is providing the ultraviolet-ray shielding composition which gives the processed article excellent in the ultraviolet-ray shielding effect.
As a result of intensive studies to solve the above-mentioned problems, the present inventors have absorbed ultraviolet rays by subjecting each of the reactive groups of the polymer and the ultraviolet absorber having reactive groups that undergo a condensation reaction to each other to undergo a condensation reaction. A UV-absorber composition in which a polymer-bonded UV absorber in which an agent is bonded to a polymer chain is combined with fine-particle white inorganic pigments such as fine-particle titanium oxide and fine-particle zinc oxide as an inorganic UV-absorber It discovered that the said subject could be achieved by mix | blending with media, such as a polymer. The present invention has been completed on the basis of this finding. In the production of a polymer-bound ultraviolet absorber, a polymer-bound ultraviolet absorber obtained by selecting an ultraviolet absorber and a polymer to be reacted with each other is obtained. It can be an appropriate (compatible) polymer-bound ultraviolet absorber for polymer components such as synthetic resins to which it is added, and is an inorganic ultraviolet absorber, such as fine particle titanium oxide or fine particle zinc oxide In combination with conventional UV absorbers, it has better compatibility with various synthetic resins, etc., excellent workability, physical properties, bleed resistance and transparency, and is extremely useful in practical use. An ultraviolet-absorbing composition can be provided.

According to the present invention, a polymer in which the ultraviolet absorber obtained by condensing each reactive group of a polymer and an ultraviolet absorber each having a reactive group that undergoes condensation reaction with each other is bonded to the polymer chain. An ultraviolet shielding composition comprising a combined ultraviolet absorber, an ultraviolet absorbing organic functional agent, and an ultraviolet absorbing inorganic pigment, wherein the ultraviolet absorbing organic functional agent is the polymer-bonded ultraviolet absorber described above, and absorbs ultraviolet rays. An ultraviolet absorbent composition is provided in which the inorganic inorganic pigment is an ultraviolet-absorbing fine particle white inorganic pigment.
Further, according to the present invention, an ultraviolet shielding composition characterized in that at least the ultraviolet absorbent composition described above is blended in a medium, and a process characterized by being formed using the composition. Articles are provided.

  The polymer-bonded ultraviolet absorber of the present invention is a synthetic resin, fiber, paper, non-woven fabric, paint, as an ultraviolet absorber composition alone or in combination with an inorganic ultraviolet absorber such as fine particle zinc oxide or fine particle titanium oxide. By adding to coating agents, textile printing agents, printing inks, electrophotographic developers, inkjet inks, adhesives or cosmetics, etc., the light produced by synthetic resin moldings and the above-mentioned processed articles by the action of sunlight, particularly ultraviolet rays, etc. It is possible to prevent / suppress the decrease in elasticity due to embrittlement due to exposure, the decrease in tensile strength, the decrease in physical properties such as the occurrence of cracks, the deterioration in electrical properties, the coloring, the discoloration of pigments such as pigments and dyes, and the fading. Furthermore, it is a defect of ordinary low molecular weight UV absorbers, such as evaporation, volatilization and sublimation, etc. This prevents or suppresses the reduction of the effective addition amount due to the blooming phenomenon, the contamination of other articles, the inhibition of printability, and the decrease in transparency due to the addition of an inorganic ultraviolet absorber to the resin. In the case of cosmetics, human skin is protected from ultraviolet rays by making use of the cosmetics.

Next, the present invention will be described in more detail.
The polymer-bound ultraviolet absorber of the present invention is obtained by condensing each of the reactive groups of the polymer and the ultraviolet absorber each having a condensation reactive group (hereinafter sometimes referred to as a reactive group). The UV absorber is a high molecular weight UV absorber bonded to a polymer chain.

  Examples of the condensable reactive group possessed by the ultraviolet absorber and the polymer include a hydroxyl group, a carboxyl group, an acid halide group, an acid anhydride group, a lower alkyl (C1 to C3) ester group, an epoxy group, an amino group, and chloro. Known reactive groups such as a triazine group or an isocyanate group may be mentioned. Examples of combinations of reactive groups include reactions of hydroxyl groups that condense to form ester bonds and carboxyl groups and derivatives thereof, and combinations of hydroxyl groups and isocyanate groups that condense (add) to form urethane bonds. The sex groups are selected as a combination of groups that undergo a condensation reaction with each other. The term “condensation” in the present invention has the meaning described in the section of “Condensation of Shukugo Condensation” in Chemical Dictionary (Kyoritsu Publishing Co., Ltd., published on March 30, 1960), Volume 4, page 682. Includes additions.

  As the ultraviolet absorber having a reactive group, a derivative obtained by introducing the above reactive group into a known ultraviolet absorber is used. For example, 3- [3 ′-(2 ″ H-benzotriazol-2 ″ -yl) -4′-hydroxyphenyl] propionic acid, 3- [3 ′-(2 ″ H-benzotriazol-2 ″ -yl) -5'methyl-4'-hydroxyphenyl] propionic acid, 3- [3 '-(2 "H-benzotriazol-2" -yl) -5'-ethyl-4'-hydroxyphenyl] propionic acid, 3- [3 '-(2 "H-benzotriazol-2" -yl) -5'-t-butyl-4'-hydroxyphenyl] propionic acid, 3- [3'-(5 "-chloro-2" H- Benzotriazol-2 "-yl) -5'-t-butyl-4'-hydroxyphenyl] propionic acid, 3- [3"-(2 "H-benzotriazol-2" -yl) -4 "-hydroxy- 5 "-(1 ', 1'-dimethyl Ndyl) phenyl] propionic acid, 3- [3 "-(2" H-benzotriazol-2 "-yl) -4" -hydroxy-5 "-(1", 1 ", 3", 3 "-tetramethyl) Butyl) phenyl] propionic acid, 4- [3 ′-(2 ″ H-benzotriazol-2 ″ -yl) -3′-hydroxyphenoxy] butyric acid and the like, their acid chlorides, and the acid group of the above compound is a hydroxyl group Derivatives of benzotriazole ultraviolet absorbers such as

2- [4 '-[(2 "-hydroxy-3" -methyloxypropyl) oxy] -2'-hydroxyphenyl] -4,6-bis (2', 4'-dimethylphenyl) -1,3 5-Triazine, 2- [4 '-[(2 "-hydroxy-3" -isopropyloxypropyl) oxy] -2'-hydroxyphenyl] -4,6-bis (2', 4'-dimethylphenyl)- 1,3,5-triazine, 2- [4 '-[(2 "-hydroxy-3" -dodecyloxypropyl) oxy] -2'-hydroxyphenyl] -4,6-bis (2', 4'- Dimethylphenyl) -1,3,5-triazine, 2- [4 ′-[(2 ″ -hydroxy-3 ″ -tetradecyloxypropyl) oxy] -2′-hydroxyphenyl] -4,6-bis (2 ', 4'-Dimethylphenyl -1,3,5-triazine, 2- [4 '-[(2 "-hydroxy-3" -octyloxypropyl) oxy] -2'-hydroxyphenyl] -4,6-bis (2', 4 '-Dimethylphenyl) -1,3,5-triazine, 2- [4'-[(2 "-hydroxy-3" -propyloyloxypropyl) oxy] -2'-hydroxyphenyl] -4,6-bis (2 ', 4'-dimethylphenyl) -1,3,5-triazine, 2- [4'-[(2 "-carboxypropoxy-3" -dodecyloxypropyl) oxy] -2'-hydroxyphenyl] -4,6-bis (2 ', 4'-dimethylphenyl) -1,3,5-triazine, 2- [4'-[(2'-phthalyloxy-3'-dodecyloxypropyl) oxy] -2 ' -Hydroxyphenyl] 4,6-bis (2 ', 4'-dimethylphenyl) -1,3,5-triazine, their dicarboxylic acid half ester derivatives, derivatives of triazine ultraviolet absorbers, such as their acid chlorides compound,

2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4,4'-di-hydroxybenzophenone, 2,2'-di-hydroxy-4,4'-di-methoxybenzophenone, Derivatives of benzophenone ultraviolet absorbers such as 2,2 ', 4,4'-tetrahydroxybenzophenone, derivatives of benzoic ultraviolet absorbers such as benzoic acid, p-aminobenzoic acid and p-dimethylaminobenzoic acid, Keihi Examples thereof include derivatives of citric acid-based ultraviolet absorbers such as acid and p-methoxycinnamic acid, and salicylic acid-based ultraviolet absorber derivatives such as salicylic acid and acid chlorides thereof.
These ultraviolet absorber derivatives can be used alone or in combination of two or more of the same or different types of the above derivatives.

  The polymer having a reactive group that condenses with the reactive group of the ultraviolet absorber is not particularly limited, and can be appropriately selected according to the type of the polymer component into which the polymer-bound ultraviolet absorber is blended. For example, a poly (ethylene-co-vinyl alcohol) copolymer, a poly (ethylene-co-vinyl alcohol-co-vinyl acetate) copolymer, a hydroxyl group-containing polyolefin polymer such as polyethylene monoalcohol; -Acrylic acid) copolymer, poly (ethylene-co-methacrylic acid) copolymer, carboxyl group-containing polyolefin polymer such as polyethylene monocarboxylic acid; poly (ethylene-co-methyl acrylate) copolymer, Polyolefin polymers having lower alkyl ester groups such as poly (ethylene-co-methyl methacrylate) copolymer; hydroxyl groups and carboxyls such as poly (ethylene-co-vinyl alcohol-co-methacrylic acid) copolymers Group-based polyolefin polymer; poly (ethylene-co-ethylene) Polyolefin having an acid anhydride group such as poly (ethylene-co-maleic anhydride) copolymer, poly (ethylene-co-butyl acrylate-co-maleic anhydride) copolymer, polyethylene-maleic anhydride graft copolymer, etc. A polyolefin polymer having an epoxy group such as a poly (ethylene-co-glycidyl methacrylate) copolymer;

Polyether polymers having hydroxyl groups such as polypropylene glycol, poly (ethylene glycol-co-propylene glycol), (polyethylene glycol)-(polypropylene glycol) block copolymers, polytetramethylene glycol; 2-hydroxyethyl (meth) Hydroxyl group-containing (meth) acrylates such as acrylate, hydroxypropyl (meth) acrylate, amino group-containing (meth) acrylates such as aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, (meth) acrylic acid, maleic acid, anhydrous Carboxyl group-containing monomers such as mono-lower alkyl esters of unsaturated dicarboxylic acids such as maleic acid, itaconic acid, monomethyl maleate and monoethyl itaconic acid; epoxies such as glycidyl (meth) acrylate A copolymer of at least one group-containing monomer and the like, and at least one kind of vinyl monomer such as styrene, acrylonitrile, vinyl chloride, (meth) acrylic acid lower alkyl ester; fat such as polybutylene adipate and polyethylene sebacate Polyester polymers such as aromatic polyesters such as aromatic polyester, polyethylene isophthalate, polybutylene terephthalate, polyneopentyl terephthalate; polyamide polymers such as 6-nylon and 6,6-nylon; hydroxyl groups and amino groups Polysilicone polymer having; polyurethane polymer; polyurea polymer; epoxy resin; melamine resin; cellulose polymer; chitosan polymer.
The number average molecular weight of the polymer having these condensable reactive groups is usually about 3,000 to 200,000, preferably about 5,000 to 100,000. Particularly preferred polymer-bonded UV absorbers in the present invention are those in which a benzotriazole UV absorber having a hydroxyl group or a carboxyl group as a reactive group is bonded to a polymer having a reactive group that undergoes a condensation reaction with these groups. .

  A method for bonding the ultraviolet absorbent having the reactive group to the polymer having the reactive group is not particularly limited. For example, these may be dissolved in a solvent for dissolving the polymer and the ultraviolet absorbent. , A method of reacting at a temperature of about 150 to 250 ° C. if necessary using a condensation catalyst, kneading the polymer and the ultraviolet absorber in a kneading machine such as an extruder under melting, and if necessary, in the presence of a condensation catalyst And the like. The amount of the UV absorber to be bonded also varies depending on the average molecular weight of the polymer. If the binding amount is small, the blending amount of the polymer-bound UV absorber increases, and if the binding amount is large, the blending amount may be small. . Therefore, although the amount of the ultraviolet absorber bonded cannot be generally defined, the amount of the bond usually ranges from 10 to 50 parts by mass as the ultraviolet absorber residue with respect to 100 parts by mass of the polymer. preferable.

（式中のＲ₁は水素または炭素数が１〜１８のアルキル基または芳香環を含むアルキル基、Ｘは炭素数が１〜１８のアルキル基またはアルコキシ基またはハロゲン元素を表す。） In the present invention, the term “ultraviolet absorber residue” refers to a residue including a structural portion involved in ultraviolet absorption in each ultraviolet absorber, and refers to the following portions.
For example, in benzotriazole ultraviolet absorbers,

(In the formula, R ₁ represents hydrogen, an alkyl group having 1 to 18 carbon atoms, or an alkyl group containing an aromatic ring, and X represents an alkyl group having 1 to 18 carbon atoms, an alkoxy group, or a halogen element.)

（式中のＲ₂、Ｒ₃は水素または炭素数が１〜４のアルキル基を表す。） For example, with a triazine UV absorber,

(R ₂ and R ₃ in the formula represent hydrogen or an alkyl group having 1 to 4 carbon atoms.)

（式中のＲ₁〜Ｒ₃は前記の定義と同じである。） For example, in benzophenone ultraviolet absorbers,

(R _{1 to} R ₃ in the formula are the same as defined above.)

  The ultraviolet absorbent composition of the present invention comprises the above-mentioned polymer-bound ultraviolet absorbent as an ultraviolet absorbent organic functional agent and an ultraviolet absorbent fine white inorganic pigment which is an ultraviolet absorbent inorganic pigment.

As the ultraviolet absorbing fine particle white inorganic pigment used in the present invention, fine particle zinc oxide and / or fine particle titanium oxide and the like are preferable. The fine particle zinc oxide and fine particle titanium oxide are preferably fine particle pigments having an average particle diameter of 5 to 100 nm, more preferably 10 to 70 nm, and a specific surface area of 20 to 80 m ² / g. These include conventionally known inorganic materials such as silica, alumina and zirconia, silicone, silane coupling agents, fatty acids, fatty acid metal salts, and melamine resins in order to improve physical properties, fastness, and impart affinity to the dispersion medium. It can also be used as a surface-treated product using an organic material such as

The use ratio of the polymer-bound ultraviolet absorber and the ultraviolet-absorbing fine particle white inorganic pigment is not particularly limited, but is preferably 5 to 95% by mass of the polymer-bound ultraviolet absorber and 95 to 5% by mass of the ultraviolet-absorbing fine particle white inorganic pigment. (The total of both is 100% by mass). When importance is attached to transparency and absorption of ultraviolet rays in the long wavelength region, it is preferable to increase the proportion of the polymer-bound ultraviolet absorber. Further, when importance is attached to the absorption of ultraviolet rays in the short wavelength region, it is preferable to increase the proportion of the ultraviolet absorbing fine-particle white inorganic pigment.
Even if the above-mentioned two components are mixed in advance, the ultraviolet absorber of the present invention contains the two components in the medium by mixing the medium and each component independently or together during use. It does n’t matter.

The ultraviolet shielding composition of the present invention is obtained by blending the above-described ultraviolet absorbent composition in a medium. Examples of the medium in the present invention include polymers (solid, solution, dispersion), cosmetic base materials, and the like.
The polymer is appropriately selected according to the purpose of use of the ultraviolet shielding composition of the present invention, and is not particularly limited. Examples of the polymer include polyethylene resin, polypropylene resin, poly (meth) acrylic ester resin, polystyrene resin, styrene-acrylonitrile resin, acrylonitrile-butadiene-styrene resin, polyvinyl chloride resin, poly Vinylidene chloride resin, polyvinyl acetate resin, polyvinyl butyral resin, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol resin, polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT), liquid crystal polyester resin (LCP), polyacetal resin (POM), polyamide resin (PA), polycarbonate resin, polyurethane resin and polyphenylene sulfide resin (PPS), natural rubber, selected from the group consisting of various synthetic rubbers One or more polymer blends or polymer alloys, and the like.

  In the ultraviolet shielding composition of the present invention, various additives used for each application can be appropriately blended depending on the purpose of use. For example, when the medium is a polymer, other functional agents such as conventionally known antioxidants, light stabilizers, infrared absorbers and antistatic agents other than the above, and various additives depending on applications, if necessary. Can also be suitably blended. These functional agents can also be used as a polymer-binding functional agent in the same manner as the polymer-bonded ultraviolet absorber.

  As a functional agent having a reactive group (same as the above-mentioned reactive group) used for forming a polymer binding functional agent, for example, as an antioxidant, 3- (3 ′, 5′-di-t-butyl) -4'-hydroxyphenyl) propionic acid, derivatives of hindered phenolic antioxidants such as their acid chloride compounds; 3-3'-thiobispropionic acid monododecyl ester, 3-3'-thiobispropionic acid Derivatives of sulfur-based antioxidants such as monooctadecyl esters and acid chlorides thereof. Examples of the light stabilizer include 2,2,6,6-tetramethyl-4-piperidinol, 1,2,6,6-pentamethyl-4-piperidinol, and the like, dicarboxylic acid half ester derivatives thereof, and acid chlorides thereof. And derivatives of hindered amine light stabilizers such as chemicals.

  Examples of the infrared absorber include tris- (t-octyl-naphthalene) (carboxyl-phthalo) cyanine / vanadium oxide complex, N- (o-carboxyl-p-dibutylaminophenyl) -N, N ′, N′— Infrared absorber derivatives such as tris- (p-dibutylaminophenyl) -p-phenylenediamine hexafluorophosphate are mentioned.

Examples of the antistatic agent include polyethylene glycol monomethyl ether, poly (ethylene glycol-co-propylene glycol) monomethyl ether, poly (ethylene glycol-co-propylene glycol) monobutyl ether, N, N-diethylaminoethanol, N, N-diethylaminopropanol, N, N-diethylaminoethoxy-polyethylene glycol, etc., dicarboxylic acid half ester derivatives thereof, acid chlorides thereof, 3-diethylaminopropionic acid, 2,3-epoxypropyl-dimethylamine, 2,3 -Derivatives of antistatic agents such as epoxypropyl-trimethylammonium chloride.
The polymer to which the functional agent having these reactive groups is bonded is the same as the polymer used for the production of the polymer-bound ultraviolet absorber.

Hereinafter, the ultraviolet shielding composition of the present invention in which the medium is a polymer will be described.
The ultraviolet-shielding composition of the present invention is used for the purpose of use (for example, using a molding machine to produce a film, a sheet, a fiber, a molded article (processed article) of various shapes; a solution state or a dispersion) However, in any case, it can be produced by a conventionally known method. Further, the amount of the ultraviolet absorbent composition of the present invention to be blended with the polymer also varies depending on the purpose of use of the ultraviolet shielding composition. Details of these will be described later.

  In the case where the ultraviolet shielding composition of the present invention is used for molding a synthetic resin (medium), for example, the composition includes a molding synthetic resin and the ultraviolet absorbent composition of the present invention, a mixing roll, It is kneaded with a Banbury mixer, an extruder or a kneader, and manufactured as a sheet-like master batch or a master batch pelletized with a pelletizer. In use, these are mixed with a synthetic resin for molding in accordance with a conventional method using a Henschel mixer, a super mixer, a tumbler, etc., and a desired molded product (processed) with a mixing roll, an injection molding machine, an extrusion molding machine, an inflation molding machine or the like. Goods).

  Examples of the synthetic resin for molding include conventionally known thermoplastic molding materials used for molding molded bodies, sheets, films and the like. For example, polyethylene resin, polypropylene resin, poly (meth) acrylic ester resin, polystyrene resin, styrene-acrylonitrile resin, acrylonitrile-butadiene-styrene resin, polyvinyl chloride resin, polyvinylidene chloride resin, Polyvinyl acetate resin, polyvinyl butyral resin, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol resin, polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT), liquid crystal polyester resin (LCP), polyacetal One resin selected from the group consisting of resin (POM), polyamide resin (PA), polycarbonate resin, polyurethane resin and polyphenylene sulfide resin (PPS), or a polymer of two or more resins Include blends or polymer alloys.

The molding synthetic resin can also be used as a thermoplastic molding material in which the above-mentioned natural resin contains glass fibers, carbon fibers, semi-carbonized fibers, cellulosic fibers, glass beads or other fillers or flame retardants. it can.
For these thermoplastic molding materials, additives for synthetic resins conventionally used as necessary, for example, polyolefin resin fine powder, polyolefin wax, ethylene bisamide wax, metal soap, etc. are used alone. Or in combination.

  In addition, as a synthetic resin for shaping | molding, thermosetting resins, such as an epoxy resin, a melamine resin, and an unsaturated polyester resin, can also be used, for example. The thermosetting resin can be used as a thermosetting molding material containing a filler and a flame retardant such as glass fiber, carbon fiber, semi-carbonized fiber, cellulosic fiber, and glass beads in addition to the above natural resin.

  In the synthetic resin molding application, the ultraviolet absorber composition of the present invention can be added in an arbitrary amount with respect to the synthetic resin, but with respect to 100 parts by mass of the synthetic resin, Usually, about 0.05 to 20 parts by mass, preferably about 0.1 to 10 parts by mass is added. Furthermore, a synergistic effect can be obtained by using a conventionally known light stabilizer, antioxidant, and / or a polymer binding functional agent obtained by binding these to a polymer.

When the ultraviolet shielding composition of the present invention is used for fiber formation, a known fiber-forming polymer is used as the polymer for the medium. Examples of the fiber-forming polymer include polyethylene terephthalate, polyamide, polypropylene, polyethylene, acrylonitrile-based polymer, polyurethane, vinyl chloride-based polymer, vinylidene chloride-based polymer, and the like. When fibers are obtained by melt spinning, the ultraviolet ray shielding composition of the present invention is used as a pelletized composition, for example, as in the case of the synthetic resin molding described above, and when fibers are obtained by wet spinning. Is used in a state in which the ultraviolet absorbent composition of the present invention is dissolved and dispersed in a spinning solution of a fiber-forming polymer. A conventionally known spinning method is used for fiber formation.
In this case, the ultraviolet absorbent composition of the present invention is preferably added in an amount of about 0.1 to 5 parts by mass with respect to 100 parts by mass of the fiber-forming polymer.

When the ultraviolet ray shielding composition of the present invention is used for paper, non-woven fabric, fiber, paint, coating agent, printing agent, printing ink, adhesive, etc., which are processed articles as referred to in the present invention, Conventionally used polymers are used as the medium. In this case, the composition of the present invention is used as a solution or a dispersion, and these are produced by a conventionally known wet processing method.
Examples of the wet processing method include a method using a heated stirring reaction tank and a mixed stirring reaction tank, a dissolver mixing method, and the like for the production of the solution. The processing method by wet dispersion includes a mixing roll mill, a kneader, a ball mill, an attritor, Sand mills, horizontal medium dispersers, vertical medium dispersers, continuous horizontal medium dispersers, continuous vertical medium dispersers, and the like are used. Moreover, it can also be set as a solution state or a dispersion composition by said wet processing method using the composition of a sheet form or a pellet form similarly to the synthetic resin shaping | molding.

As the medium polymer (coating film forming component) in the paint, when the paint is an oil-based solvent type, for example, conventionally known acrylic melamine resins, alkyd melamine resins, polyester melamine resins, acrylic isocyanate resins For example, an acrylic resin, an alkyd melamine resin, etc., for an aqueous solution type paint, an acrylic resin, a fluorine resin, etc. For example, acrylic isocyanate resins, polyester isocyanate resins, polyester epoxy resins, and the like, and ultraviolet / electron beam curable paints include urethane acrylate resins, epoxy acrylate resins, polyester acrylate resins, and the like. The paint using the ultraviolet shielding composition of the present invention is suitable for metal plates, particularly for automobiles, coil coatings, building materials, and woodworking.
In addition, also when using the ultraviolet-shielding composition of this invention for manufacture of a coating agent or an adhesive agent, the usage-amount of a manufacturing method and a ultraviolet absorber composition is the same as that of the case of a coating material.

  When the ultraviolet shielding composition of the present invention is used as a printing agent (usually a dispersion), examples of the polymer for the medium include conventionally known acrylic resins, acrylic-styrene resins, and synthetic rubbers. . These are used in the form of emulsions.

When the ultraviolet shielding composition of the present invention is used for various printing inks, a conventionally known vehicle polymer for printing ink is used as the medium polymer.
Examples of the printing ink include conventionally known rotary inks, offset inks such as sheets, gravure inks for plastic films and sheets, aluminum foils, building materials and decorative plates, and inks for metal plates. The composition of the present invention can also be used in the production of electrophotographic developers and inkjet inks. For example, conventionally known full-color, mono-color, and monochrome dry developers, wet developers, water-based, oil-based, and solid-type inkjet inks can be used. The above composition of the present invention is particularly suitable for the production of developers and inks used for full color image applications such as advertisements, signboards, and exterior coatings.

  A colorant can be added to the ultraviolet shielding composition of the present invention depending on the application. The coloring agent is not particularly limited, and a coloring agent conventionally used for coloring an article such as coloring of a synthetic resin, paint, printing agent, printing ink, electrophotographic developer or inkjet ink is used. As the pigment, for example, commonly used organic pigments, inorganic pigments, extender pigments and dyes are used. Specifically, for example, soluble azo pigments, insoluble azo pigments, polyazo pigments, azomethine azo pigments, anthraquinone pigments, phthalocyanine pigments, quinacridone pigments, perinone-perylene pigments, azomethine pigments, isoindolinones Pigments, organic pigments such as pyrrolopyrrole pigments, fluorescent pigments, carbon black pigments, titanium oxide pigments, yellow iron oxides, petals, chromium oxides, ultramarine blues, complex oxide pigments, inorganic pigments such as zinc sulfide, calcium carbonate And extender pigments such as talc, kaolin and barium sulfate, and further disperse dyes and oil-soluble dyes.

  The use of the ultraviolet absorbent composition of the present invention is effective in improving durability against discoloration, discoloration, etc. of the pigment, and for this purpose, as described above, the coloring composition for synthetic resin, paint, printing agent, printing ink, electronic A method of adding and mixing the ultraviolet absorber composition and the dye to the polymer at the time of adjusting a coloring composition such as a photographic developer or inkjet ink, or mixing the dye with the ultraviolet absorber composition in advance during the production process of the dye Alternatively, a method of coating with an ultraviolet absorbent composition and using it as a processed pigment product can be used. Depending on the purpose, a plurality of polymer binding functional agents can be used in combination, or in the case of coating treatment, they can be processed into micropolymer beads, or the polymer binding functional agent can be fixed to the dye by crosslinking treatment, etc. It is also effective.

  The ultraviolet absorbent composition of the present invention can be used for sunscreen products of medicinal cosmetics. In this case, examples of the polymer-bound ultraviolet absorber include benzoic acid-based ultraviolet absorber derivatives such as benzoic acid, p-aminobenzoic acid and p-dimethylaminobenzoic acid having the above-mentioned condensable reactive groups, cinnamic acid, p -What is obtained by condensing an ultraviolet absorber derivative such as a cinnamate-based ultraviolet absorber derivative such as methoxycinnamic acid, salicylic acid or the like and an acid chloride thereof with a polymer having the above-described condensable reactive group. used. The ultraviolet absorbent composition of the present invention is highly safe to the skin and has the ability to effectively absorb UV-A (320 to 400 nm) and UV-B (290 to 320 nm) harmful to the skin. , Creams, milky lotions, oils, lotions, and the like, which are required to be evenly mixed with sweat and water baths, and more stable. The amount to be blended is not generally determined depending on the condition of skin exposure, the purpose of use, the material used, etc., but it is converted into a UV-absorbent material in cosmetics (UV-absorber in polymer-bound UV-absorber) Used in an amount of about 1 to 20% by weight).

  The ultraviolet absorbent composition combining the polymer-bound ultraviolet absorbent of the present invention and the fine particle zinc oxide is excellent in absorption of ultraviolet rays in the A region and B region, and has a large transmittance in the visible light region and excellent transparency. Yes. Further, since the ultraviolet absorbent composition of the present invention is excellent in solvent resistance and bleed resistance and has high transparency, it is useful for the production of a UV shielding composition excellent in a wide range of UV shielding effects and processed articles thereof. It is.

  EXAMPLES Next, although a synthesis example and an Example are given and this invention is demonstrated further more concretely, this invention is not limited at all by these examples. In addition, the part or% in the sentence is based on mass.

Example 1
(1) 259 parts of 3- [3 '-(2 "H-benzotriazol-2" -yl) -5-tert-butyl-4'-hydroxydiphenyl] propionic acid and ethylene-vinyl alcohol copolymer (vinyl alcohol Content: 16.8%, number average molecular weight: 16,000) 200 parts were dissolved in xylene and subjected to a condensation reaction at 220 ° C. for 5 hours to obtain a polymer-bound ultraviolet absorber.
The content of the ultraviolet absorbent residue in the obtained polymer-bound ultraviolet absorbent is the content in terms of 3- (2′H-benzotriazol-2′-yl) -5-tert-butyl-4-hydroxyphenol group. In terms of rate, it is 35%.

Example 2
(1) The polymer-bound ultraviolet absorber obtained in Example 1 was blended with polyethylene resin so that the content of the ultraviolet absorber residue was 10%, and the temperature of the kneading part was measured by a screw-type twin screw extruder. Was kneaded and extruded at 200 ° C. to prepare a polyethylene masterbatch containing a polymer-bound ultraviolet absorber.

(2) Separately, 20% of fine zinc oxide (primary particle size 0.02 μm: conversion from BET value) is blended with polyethylene resin, and kneaded and extruded at a kneading part temperature of 200 ° C. with a screw type twin screw extruder. A polyethylene masterbatch containing fine particle zinc oxide was prepared.

(3) 15 parts of the polymer-bound ultraviolet absorber-containing polyethylene masterbatch obtained in (1) above and 10 parts of the fine particle zinc oxide-containing polyethylene masterbatch obtained in (2) above were mixed and mixed with 75 parts of polyethylene resin. A kneading and melting at 200 ° C. with a screw rotation speed of 50 rpm using a screw type extruder, extruded from a circular die into a cylindrical shape, and formed into a film of 50 μm thickness by an inflation method. An ultraviolet shielding polyethylene resin film containing 1.5% of the combined ultraviolet absorber and 1.0% of the fine zinc oxide was obtained.

Example 3
15 parts of a polymer-bound ultraviolet absorber-containing polyethylene masterbatch obtained in Example 2 (1) and 15 parts of a fine particle zinc oxide-containing polyethylene masterbatch obtained in Example 2 (2) were blended with 70 parts of a polyethylene resin. Using a screw type extruder, the mixture is kneaded and melted at 200 ° C. at a screw speed of 50 rpm, extruded from a circular die into a cylindrical shape, and formed into a 50 μm thick film by an inflation method. An ultraviolet shielding polyethylene resin film containing 1.5% of the coalesced ultraviolet absorber and 1.5% of the fine zinc oxide was obtained.

Comparative Example 1
20 parts of the polymer-bound ultraviolet absorber-containing polyethylene masterbatch obtained in Example 2 (1) was blended and mixed with 80 parts of a polyethylene resin, and the mixture was mixed at 200 ° C. using a screw extruder at a screw speed of 50 rpm. Were kneaded and melted, extruded into a cylindrical shape from a circular die, and formed into a film having a thickness of 50 μm by an inflation method, to obtain an ultraviolet shielding polyethylene resin film containing 2% of a polymer-bound ultraviolet absorber. .

Comparative Example 2
20 parts of the fine-particle zinc oxide-containing polyethylene masterbatch obtained in Example 2 (2) was blended with 80 parts of polyethylene resin, mixed, and kneaded and melted at 200 ° C. at a screw speed of 50 rpm using a screw type extruder. Then, this was extruded into a cylindrical shape from a circular die and formed into a film having a thickness of 50 μm by an inflation method to obtain an ultraviolet shielding polyethylene-based resin film containing 4% of fine particle zinc oxide.

Comparative Example 3
3 parts of the polymer-bound UV absorber-containing polyethylene masterbatch obtained in Example 2 (1) was blended with 97 parts of polyethylene resin, mixed, and then used at 200 ° C. at a screw rotation speed of 50 rpm using a screw type extruder. Kneaded and melted with a circular die and formed into a film having a thickness of 50 μm by an inflation method. An ultraviolet shielding polyethylene resin film containing 0.3% of a polymer-bonded ultraviolet absorber Obtained.

Comparative Example 4
(1) A commercially available benzotriazole-based low molecular weight UV absorber is blended in 10% of polyethylene resin, and kneaded and extruded at a kneading part temperature of 200 ° C. with a screw-type twin screw extruder, and a polyethylene master containing a low molecular weight UV absorber. Created a batch.
(2) 3 parts of the low molecular weight ultraviolet absorber-containing polyethylene masterbatch obtained in (1) above was blended and mixed with 97 parts of polyethylene resin and 200 ° C. at a screw rotation speed of 50 rpm using a screw type extruder. UV-shielding polyethylene resin film containing 0.3% of a commercially available low molecular weight UV absorber, which is kneaded and melted in a cylinder, extruded into a cylindrical shape from a circular die, and formed into a film having a thickness of 50 μm by an inflation method. Got.

(Test method)
In order to evaluate ultraviolet ray shielding ability and transparency to visible light using the ultraviolet ray shielding polyethylene-based resin films obtained in the above examples and comparative examples, and to observe the durability to organic solvents A dissolution test in a solvent was conducted. The test method is as follows.

(1) Light transmittance measurement The light transmittance with a wavelength of 200 to 500 nm is measured with a spectrophotometer (manufactured by Hitachi). The light transmittance of the B region ultraviolet ray having a wavelength of 265 nm, the wavelength of 300 nm, the A region ultraviolet ray having a wavelength of 350 nm and 385 nm, and the visible region of 500 nm was measured to evaluate the shielding ability against ultraviolet rays and the transparency to visible light. The results are shown in Table 1.

As is clear from Table 1, the polyethylene film containing the ultraviolet absorbent composition combining the polymer-bound ultraviolet absorbent of the present invention of Examples 2 and 3 and the fine particle zinc oxide is the polymer-bound ultraviolet light of Comparative Example 1. Compared to a polyethylene film containing an absorbent alone, it absorbs ultraviolet rays even in a short wavelength region of 300 nm or less.
Further, the film containing the ultraviolet absorbent composition of the present invention of Examples 2 and 3 was 300 nm in the B wavelength region, 350 nm and 385 nm compared to the film containing only the fine particle zinc oxide of Comparative Example 2. It has excellent absorption of ultraviolet rays in the A wavelength region, has a large visible light transmittance of 500 nm, and is excellent in transparency.
Therefore, the polyethylene film blended with the ultraviolet absorbent composition of the present invention of Examples 2 and 3 is superior to the film blended with the fine particle zinc oxide of Comparative Example 2 alone, and absorbs visible light. Is large and excellent in transparency. In particular, the polyethylene film of Example 2 is a film having a blending formula that emphasizes transparency, and Example 3 is the film having a blending formula that prioritizes ultraviolet shielding.

(2) Organic solvent elution test Polyethylene film in which the ultraviolet absorbent composition of the present invention of Example 2 was blended, polyethylene film in which only fine particulate zinc oxide in Comparative Example 2 was blended, and polymer-bound ultraviolet absorption in Comparative Example 3 A polyethylene film containing only an agent and a polyethylene film containing a commercially available benzotriazole-based low molecular weight ultraviolet absorber of Comparative Example 4 were immersed in various organic solvents listed in Table 2 for 48 hours, and then the film was measured with a spectrophotometer. The residual absorption rate at the maximum absorption wavelength was measured. The results are shown in Table 2.

As is apparent from Table 2, low molecular weight UV absorbers are easily eluted in various solvents, whereas polymer-bound UV absorbers and fine particle zinc oxide are solvent resistant and bleed resistant to various solvents. Is excellent. Therefore, the ultraviolet absorbent composition of the present invention combining them is excellent in elution resistance and bleed resistance against various solvents.

Claims (10)

  An ultraviolet absorber having a reactive group capable of undergoing a condensation reaction with each other and the ultraviolet absorber obtained by condensing each reactive group of the polymer are bonded to the polymer chain. Combined UV absorber.   2. The weight according to claim 1, wherein the ultraviolet absorber is at least one selected from the group consisting of benzotriazole-based, triazine-based, benzophenone-based, benzoic acid-based, cinnamic acid-based and salicylic acid-based ultraviolet absorbers. Combined UV absorber.   In the ultraviolet absorbent composition comprising the ultraviolet absorbing organic functional agent and the ultraviolet absorbing inorganic pigment, the ultraviolet absorbing organic functional agent has a reactive group that undergoes a condensation reaction with each other. The ultraviolet absorber obtained by condensing a group is a polymer-bound ultraviolet absorber bonded to the polymer chain, and the ultraviolet absorbing inorganic pigment is an ultraviolet absorbing fine particle white inorganic pigment Ultraviolet absorber composition.   The ultraviolet absorbent composition according to claim 3, wherein the ultraviolet absorbing fine particle white inorganic pigment is a fine particle zinc oxide pigment and / or a fine particle titanium oxide pigment having an average particle diameter of 5 to 100 nm.   An ultraviolet shielding composition comprising the medium and at least the ultraviolet absorbent composition according to claim 3.   6. The ultraviolet light shielding composition according to claim 5, wherein the ultraviolet absorbent composition according to claim 3 is kneaded with a medium, or dissolved and dispersed in a medium solution or an aqueous dispersion. Production method.   An ultraviolet light shielding processed article formed using the ultraviolet light shielding composition according to claim 5 or obtained by the method according to claim 6.   The ultraviolet light shielding processed article according to claim 7, wherein the medium is a polymer, and the processed article is selected from a molded article, paper, nonwoven fabric, fiber, and electrophotographic dry developer.   A printing agent, a paint, a coating agent, an adhesive, a printing ink, an inkjet ink, and an electronic medium comprising a polymer as a medium and a processed article comprising a solution or an aqueous dispersion of an ultraviolet shielding composition obtained by the method according to claim 6. The ultraviolet shielding processed article according to claim 7, which is selected from photographic wet developers. The ultraviolet light shielding processed article according to claim 7, wherein the medium is a cosmetic base material and the processed article is a cosmetic.