JP2007297494A - Ultraviolet shielding composition, method of manufacturing the same, method of using the composition, and articles using the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ultraviolet shielding composition in which a polymer-bonded ultraviolet absorbing agent is dispersed in a dispersing medium such as a resin, and which is superior in ultraviolet shielding effect, high in transparency and superior in anti-bleeding property. <P>SOLUTION: The ultraviolet shielding composition is characterised by being formed by dispersing the polymer-bonded ultraviolet absorbing agent obtained by reacting an ultraviolet absorbing agent having a reactive group with a polymer having a group having reactivity with the reactive group, in the dispersing medium. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is an ultraviolet shielding material in which a polymer-bound ultraviolet absorber is dispersed in a dispersion medium such as a resin (including synthetic, semi-synthetic and natural resins), which has an excellent ultraviolet shielding effect, high transparency, and excellent bleed resistance. The present invention relates to a composition, a method for producing the composition, a method for using the composition, and an article using the composition.

  When plastics molded products are used or stored for a long period of time, the elasticity decreases due to embrittlement due to exposure to sunlight, especially ultraviolet rays, the tensile strength decreases, the physical properties such as the occurrence of cracks, the electrical properties deteriorate, Causes coloring. Similarly, a resin coating film composed of a coating agent such as a coating agent, a paint, an offset ink, a gravure ink, and a printing agent causes gloss reduction, cracking, blistering, discoloration of the pigment, fading, and the like due to the exposure to ultraviolet rays. Moreover, in the resin packaging material, if the packaging material is inappropriate, the packaged contents cause quality deterioration due to ultraviolet rays or the like.

  In order to improve these problems, UV absorbers, especially benzotriazole UV absorbers, triazine UV absorbers, salicylate UV absorbers, benzophenone UV absorbers, etc. are used to prevent resin degradation. Yes. These ultraviolet absorbers are used alone or in combination with an antioxidant, a light stabilizer such as a hindered amine, and the like, and an antistatic agent is used in combination for the purpose of antistatic.

  However, since these ultraviolet absorbers are generally low molecular weight compounds, there are various disadvantages in using them. For example, in the case of ultraviolet absorbers having a relatively low melting point or sublimable ultraviolet absorbers, ultraviolet rays may be used during the heat processing such as molding processing or heat curing of the resin containing them, or during storage or use in a heated state. The UV absorber may be extracted from the resin or coating film when the absorber causes sublimation or volatilization, or comes in contact with warm water, aqueous solutions such as acidic or alkaline, or organic solvents such as alcohol or oil. In some cases, the effect of the UV absorber cannot be sustained over a long period of time.

  Also, when the UV absorber is mixed with the resin, if the compatibility with the resin is poor, the UV absorber will bleed out (blooming phenomenon) on the surface of the molded product or the painted surface during long-term use. In addition to reducing the effective abundance in the resin, it causes stickiness on the surface of molded products, etc., decreases the adhesion and printability of the surface, and bleed-out UV absorbers contaminate other articles. Such problems may occur. Furthermore, if a large amount of UV absorber is added to the resin, the UV absorber will cause phase separation and reduce the transparency and mechanical strength of the resin, so the amount of UV absorber added to the resin is limited. There was a need for improvement. In addition, because UV absorbers are small molecules, irritation to the skin and mucous membranes is observed, and when UV absorbers are powders, attention should be paid to safety and hygiene such as dust generation. There is something.

  Therefore, the methacryloyl group is added to the UV absorber, and this is copolymerized with other methacrylic ester monomers and styrene monomers to increase the molecular weight of the UV absorber and prevent volatilization and elution of the UV absorber. Attempts have been made. However, it has been difficult to avoid that the polymerizable group such as the methacryloyl group is gradually polymerized even during storage. Further, as a practical problem, the above-mentioned copolymer is an acrylic, methacrylic, styrene, vinyl acetate or the like copolymer, and the copolymer is a main resin such as polyethylene or polypropylene. Depending on the type of resin, such as polyolefin resins, various polyester resins, polyamide resins, polycarbonate resins, etc., the range of use is limited because the compatibility of the above-mentioned copolymer is not sufficient. As an agent, the problem has not been solved.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors bonded an ultraviolet absorber having a condensation reactive group to a polymer having a group that reacts with the reactive group by a condensation reaction. It has been found that the above-mentioned problems can be solved by the obtained polymer-bound ultraviolet absorber. The present invention has been completed based on this finding. In the production of a polymer-bound ultraviolet absorber, the polymer-bound ultraviolet absorber is added by selecting a UV absorber and a polymer to be reacted with each other. It is possible to make a polymer-bonded UV absorber suitable for the resin to be used, etc., better compatibility with various resins compared to conventional UV absorbers, excellent workability and physical properties. It is excellent in stability, bleed resistance and the like, and is extremely useful in practice by processing the polymer-bound ultraviolet absorber dispersed in a dispersion medium such as a resin.

  That is, the present invention is a polymer-bonded ultraviolet absorber obtained by reacting an ultraviolet absorber having a reactive group with a polymer having a group that reacts with the reactive group, the ultraviolet absorber described above. UV absorption of benzotriazole type, triazine type, benzophenone type, benzoic acid type, cinnamic acid type and salicylic acid type having at least one group selected from carboxylic acid alkyl ester group, carboxylic acid halogenide group, hydroxyl group and amino group At least one selected from the group consisting of agents, and the polymer is a polymer having at least one group selected from a hydroxyl group, an amino group, a carboxylic acid alkyl ester group and a carboxylic acid halide group, and A polymer-bound ultraviolet absorber having an ultraviolet absorber residue content of 5 to 95% by mass is dispersed in a dispersion medium. UV-screening composition, characterized in that, a method of manufacturing the same, an article using the methods for their use and their.

  In the ultraviolet shielding composition of the present invention, the polymer-bound ultraviolet absorber constituting the composition is more compatible with various resins than the conventional ultraviolet absorber, and has excellent processability. Since it is excellent in thermal stability and bleed resistance, it has excellent physical properties such as processability, thermal stability and bleed resistance of the processed article.

  The ultraviolet shielding composition of the present invention is characterized by excellent compatibility with the resin and coating material used as a physical property deterioration improving agent for the resin and coating material. UV absorbers do not evaporate or sublimate even during heat curing of ink, etc., do not elute into water, organic solvents, etc., and UV absorbers do not bleed out to the surface of molded products or coating materials In addition to having excellent properties, the ultraviolet absorber is bonded to a high molecular weight polymer, so that it is excellent in safety and hygiene.

Next, the present invention will be described in more detail with reference to preferred embodiments.
The polymer-bound ultraviolet absorber used in the present invention is obtained by subjecting at least one ultraviolet absorber having a reactive group to a condensation reaction with a polymer having a group that undergoes a condensation reaction with the reactive group. Further, in some cases, an ultraviolet absorber having a reactive group and at least one functional agent such as an antioxidant, a light stabilizer, an infrared absorber, a fluorescent whitening agent, or an antistatic agent having a reactive group, It is also possible to carry out a condensation reaction with a polymer having a reactive group.

Examples of the reactive group possessed by the ultraviolet absorber or polymer include a hydroxyl group, a carboxyl group, an acid halide group of a carboxyl group, an acid anhydride group of a carboxyl group, and an alkyl (C ₁ -C ₁₂ ) ester group of a carboxyl group. , Known condensation reactive groups such as an epoxy group, an amino group, a chlorotriazine group and an isocyanate group. These reactive groups are combined such as a combination of a hydroxyl group and a carboxyl group or a derivative group thereof (ester bond), or a combination of a hydroxyl group and an isocyanate group (urethane bond).

  Examples of the ultraviolet absorber having a reactive group include 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-benzotriazole -2 "'-yl) -4" -hydroxy -5 "-(1 ', 1'-dimethylbenzyl) phenyl] propionic acid, 3- [3"-(2 "' H-benzotriazol-2" '-yl) -4 "-hydroxy-5"-( 1 ", 1", 3 ", 3" -tetramethylbutyl) phenyl "propionic acid, 4- [3 '-(2"' H-benzotriazol-2 "-yl) -3'-hydroxyphenoxy] butyric acid Or 2- (2 ′, 4′-dihydroxyphenyl) 2H-benzotriazole compounds such as 2- (2 ′, 4′-dihydroxyphenyl) 2H-benzotriazole, 5′-chloro-2 substituted with a halogen atom -(2 ', 4'-dihydroxyphenyl) 2H-benzotriazole, 5'-bromo-2- (2', 4'-dihydroxyphenyl) 2H-benzotriazole, etc., or a benzotriazole group 5'-methyl 2- (2 ', 4'-dihydroxyphenyl) 2H-benzotriazole, 5'-tbutyl-2- (2', 4 ') substituted with one or two alkyl groups from 1 to C5 -Dihydroxyphenyl) 2H-benzotriazole, 5 ', 6'-dimethyl-2- (2', 4'-dihydroxyphenyl) 2H-benzotriazole, or the like, or a benzotriazole group substituted with an alkoxy group from C1 to C5 Cyclic to 5'-methoxy-2- (2 ', 4'-dihydroxyphenyl) 2H-benzotriazole, 5'-n-butoxy-2- (2', 4'-dihydroxyphenyl) 2H-benzotriazole, etc. Ester compounds such as β-propiolactone, β-butyrolactone, γ-butyrolactone, ε-caprolactone, δ-valerolactone and γ A compound obtained by ring-opening reaction of valerolactone or the like, or a compound obtained by ring-opening condensation, specifically 3- [4 ′-(2 ″ H-benzotriazol-2 ″ -yl) -3′-hydroxyphenoxy] propion Acid, 4- [4 ′-(2 ″ H-benzotriazol-2 ″ -yl) -3′-hydroxyphenoxy] butanoic acid, 6- [4 ′-(2 ″ H-benzotriazol-2 ″ -yl) -3'-hydroxyphenoxy] hexanoic acid or the like, or polybutyrolactone or caprolactone having [4 '-(2 "H-benzotriazol-2" -yl) -3'-hydroxyphenoxy] bonded to the terminal And derivatives of benzotriazole-based ultraviolet absorbers such as acid chlorides thereof.

  Further, as another ultraviolet absorber, for example, 2- {4 "-[(2" '-chlorocarbonyl-propionyloxy) -3 "'-dodecyloxypropyloxy] -2" -hydroxyphenyl} -4, 6-bis (2 ′, 4′-dimethylphenyl) -1,3,5-triazine, 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, or 2- [4 ′-[(2 ″ -hydroxy-3 ″ -tetradecyloxypropyl) Oxy] -2'-hydroxyphenyl] -4,6-bis (2 ', 4'-dimethylphenyl) -1,3,5-triazine, 2- [4'-[(2 "-hydroxy-3"- Octyroyloxypropyl) 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 ″ -carboxypropy Xy-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, etc. Examples thereof include derivatives of triazine-based ultraviolet absorbers such as dicarboxylic acid half ester derivatives and acid chlorides thereof.

  2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n octoxybenzophenone, 4,4'-di-hydroxybenzophenone, 2,2'-di-hydroxy-4,4'-di-methoxybenzophenone, 2, Benzophenones such as 2,2 ', 4,4'-tetrahydroxybenzophenone, benzoic acids such as benzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, cinnamic acids such as cinnamic acid and p-methoxycinnamic acid And ultraviolet absorbers such as salicylic acid and acid chlorides thereof.

  As a functional agent having reactivity that may be used in combination with the above polymer-bonded ultraviolet absorber, for example, as an antioxidant, 3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) ) Derivatives of hindered phenolic antioxidants such as propionic acid and their acid chloride compounds; 3-3'-thiobispropionic acid monododecyl ester, 3-3'-thiobispropionic acid monooctadecyl ester and the like And derivatives of sulfur-based antioxidants such as acid chlorides.

  Examples of the light stabilizer include 2,2,6,6-tetramethyl-4-piperidinol, 1,2,6,6-pentamethyl-4-piperidinol, and their dicarboxylic acid half ester derivatives and their Examples include hindered amine light stabilizer derivatives such as acid chloride compounds. Examples of the infrared absorber include tris (t-octyl-naphthalene) (carboxyl-phthalo) cyanine / vanadium oxide complex, N- (o-carboxyl-p-dibutylaminophenyl) -N, N ′, N ′. -Derivatives of infrared absorbers such as -tris (p-dibutylaminophenyl) -p-phenylenediamine hexafluorophosphate.

  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 and the like and their dicarboxylic acid half ester derivatives and their acid chlorides, such as 3-diethylaminopropionic acid, 2,3-epoxypropyl-dimethylamine, 2,3 -Derivatives of antistatic agents such as epoxypropyl-trimethylammonium chloride.

  The polymer having a reactive group that reacts with the ultraviolet absorber having the reactive group is not particularly limited. For example, polyolefin polymers such as polyethylene, polypropylene, poly (ethylene-co-propylene), poly (ethylene-co-propylene-co-α-olefin), polypropylene glycol, poly (ethylene glycol-co-propylene glycol), (Polyethylene glycol)-(polypropylene glycol) block copolymers, polyether polymers such as polytetramethylene glycol, aliphatic polyesters such as polybutylene adipate and polyethylene sebacate, polyethylene isophthalate, polybutylene terephthalate, polyneopentyl Polyester polymers such as aromatic polyester such as terephthalate, polyamide polymers such as 6-nylon and 6,6-nylon, polystyrene, styrene Polymers, polyvinyl polymers such as polyvinyl butyral, acrylic acid ester (co) polymers, methacrylic acid ester (co) polymers, (meth) acrylic (co) polymers such as acrylic-styrene copolymers, and polysilicones Homopolymers selected from polymer, polyurethane polymer, polyurea polymer, epoxy resin, melamine resin, cellulose polymer, chitosan polymer or the like, or two or more of the above And a block copolymer made of the above-mentioned polymer.

  The polymer has a weight average molecular weight of about 3,000 to 200,000, preferably about 5,000 to 100,000. The polymer-bound ultraviolet absorber using these polymers is a polymer having a relatively low molecular weight, but is excellent in safety and hygiene compared to the ultraviolet absorber having a significantly lower molecular weight than the polymer, It is not volatilized even when heated during processing, storage or use of articles, does not cause blooming phenomenon, and has excellent compatibility with the resin. It can be added and does not impair the physical properties of the added resin.

Examples of the reactive group of the polymer include a hydroxyl group, a carboxyl group, an acid halide group of a carboxyl group, an acid anhydride group of a carboxyl group, an alkyl (C ₁ -C ₁₂ ) ester group of a carboxyl group, an epoxy group, and an amino group. Chlorotriazine group and isocyanate group. These reactive groups are selected in combination with the reactive group possessed by the ultraviolet absorber. As a combination of reactive groups, a combination of a hydroxyl group and a carboxyl group or carboxy chloride is particularly preferable.

  Examples of the polymer having a reactive group include a polyolefin-based reactive polymer such as a poly (ethylene-co-vinyl alcohol) copolymer, poly (ethylene-co-vinyl alcohol-co-vinyl acetate). ) Copolymer, poly (ethylene-co-acrylic acid) copolymer, poly (ethylene-co-methyl acrylate) copolymer, poly (ethylene-co-methacrylic acid) copolymer, poly (ethylene- co-methyl methacrylate) copolymer, poly (ethylene-co-vinyl alcohol-co-methacrylic acid) copolymer, poly (ethylene-co-ethyl acrylate-co-maleic anhydride) copolymer, poly (Ethylene-co-butyl acrylate-co-maleic anhydride) copolymer, polyethylene-maleic anhydride graft copolymer, Li (ethylene -co- glycidyl methacrylate) copolymer, polyethylene monoalcohol, and polyethylene monocarboxylic acid. In a vinyl polymer system, a (meth) acrylic polymer system, or the like, a reactive group can be introduced into a polymer by copolymerizing a reactive monomer at the time of producing the polymer or by performing a post-treatment after the polymerization.

  The content of the UV absorber residue in the polymer-bound UV absorber used in the present invention increases the usage amount in actual use if the amount of the UV absorber bound to the polymer is small. If the amount of the bond to the polymer is large, the amount used is small. The binding amount of the ultraviolet absorber to the polymer differs depending on the weight average molecular weight of the polymer to which the residue is bonded and cannot be generally specified. However, the preferable binding amount of the ultraviolet absorber to the polymer is The amount of the ultraviolet absorbent residue in the bound ultraviolet absorbent is such an amount that it is 5 to 95% by mass. Here, the ultraviolet absorbent residue refers to the remaining part of the ultraviolet absorbent having the reactive group exemplified above, from which the reactive group has been removed.

  The production method of the polymer-bonded ultraviolet absorber used in the present invention is not particularly limited. For example, the polymer and the ultraviolet absorber are dissolved in a solvent for dissolving them, and the reaction is carried out at a temperature of about 150 to 250 ° C. using a condensation catalyst, if necessary, in a kneader such as an extruder. Examples include a method in which the coalescence and the ultraviolet absorber are reacted in the presence of a condensation catalyst if necessary in the presence of a melt. The production methods for other polymer-binding functional agents are the same as described above.

  The ultraviolet shielding composition of the present invention is a composition in which a polymer-bound ultraviolet absorber is dispersed in a dispersion medium, for example, a resin, depending on its use, and the composition is used for production of various products. Examples of the resin as the dispersion medium include a solid or molten resin, a resin solution, or an aqueous dispersion of the resin. The ultraviolet shielding composition of the present invention using such a resin as a dispersion medium is, for example, a resin molded article, fiber, paper, nonwoven fabric, paint, coating agent, printing agent, printing ink, electrophotographic developer, inkjet ink, It can be obtained by adding a polymer-bonded UV absorber to each resin, its solution, vehicle resin or aqueous dispersion during the production of an adhesive or cosmetic. These compositions are commercialized by respective conventionally known processing methods or processing methods such as molding, spinning, and papermaking. Various products are used for film formation, coating, textile printing, printing, electrophotographic recording, ink jet printing, adhesion, and the like, and functions such as an improved ultraviolet absorption function are imparted to the formed processed articles and records.

  The above-mentioned various articles include, for example, pigments such as a decrease in elasticity due to exposure to sunlight, particularly embrittlement of the resin due to the action of ultraviolet rays, a decrease in tensile strength, a decrease in resin physical properties such as the occurrence of cracks, a deterioration in electrical properties, and coloring. Solves problems such as discoloration and discoloration of pigments such as dyes, and further degrades the compatibility of UV absorbers due to evaporation, volatilization and sublimation, which is a defect of ordinary low-molecular UV absorbers, and compatibility Limitation of additive amount due to the limit of the surface, reduction of effective additive amount due to blooming phenomenon on the surface, contamination of other articles and inhibition of printability, transparency due to addition of inorganic UV absorber to resin (polymer medium) Improves the decrease of Further, in the case of cosmetics, human skin is protected by using the cosmetics.

  Examples of the resin as the dispersion medium include polyethylene resins, polypropylene resins, poly (meth) acrylate esters, polystyrene resins, styrene-acrylonitrile resins, acrylonitrile-butadiene-styrene resins, polyvinyl chloride resins. 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), Resin selected from the group consisting of liquid crystal polyester resin (LCP), polyacetal resin (POM), polyamide resin (PA), polycarbonate resin, polyurethane resin, and polyphenylene sulfide resin (PPS) or It is a polymer blend or a polymer alloy species or more resins.

  Further, a molding material in which a filler such as glass fiber, carbon fiber, semi-carbonized fiber, cellulosic fiber, glass bead, or a flame retardant is added to the resin is also used. For example, a composite material containing engineering plastics such as PET, PBT, LCP, POM, PA, and PPS, or various additives such as a flame retardant, a foaming agent, an antibacterial agent, and a crosslinking agent are added.

  In addition, conventionally used additives for resins, for example, polyolefin resin fine powder, polyolefin wax, ethylene bisamide wax, metal soap, etc. can be used alone or in combination as required. . As thermosetting resins, epoxy resins, melamine resins, unsaturated polyester resins, etc., these resins contain fillers such as glass fibers, carbon fibers, semi-carbonized fibers, cellulosic fibers, glass beads, flame retardants, etc. A thermosetting molding material is mentioned.

  The ultraviolet shielding composition of the present invention can be obtained by adding a polymer-bound ultraviolet absorber in an arbitrary addition amount to the above resin. About 100 to 20 parts by mass, preferably about 0.1 to 10 parts by mass is added. In addition, depending on the function of the UV absorber residue as the polymer-bonded UV absorber and the purpose of use, a combination or combination of similar functional agents such as benzotriazole UV absorber and triazine UV absorber A synergistic effect can be obtained by using two or more kinds in combination including a combination of different functional agents such as a combined-bonded UV absorber and a polymer-bonded light stabilizer or a polymer-bonded antioxidant.

  The ultraviolet ray shielding composition of the present invention is kneaded with a polymer-bonded ultraviolet absorber alone or with the above-mentioned resin added in a mixing roll, a Banbury mixer, a kneader, a kneader ruder, a single screw extruder or a multi-screw extruder. , Cut into a sheet-like masterbatch or pelletized with a pelletizer, and mixed with the above resin using a Henschel mixer, super mixer, tumbler, etc. according to conventional methods, mixing roll, injection molding machine, extrusion molding It is molded by a machine, blow molding machine, inflation molding machine, compression molding machine, rotary molding machine, thermosetting resin molding machine, and the like.

  Examples of articles formed by the above method include containers, films, sheets, blisters, pipes, hoses, tubes, beads, fibers, automobile parts, electrical equipment parts, stationery, furniture, daily necessities, and the like. Among the above-mentioned articles, this is used for articles that require transparency, UV shielding, and bleed resistance, especially for foods, medical supplies, cosmetics, or packaging films and containers for precision equipment parts that require bleed resistance. The ultraviolet screening compositions of the invention are suitable.

  Examples of the fiber material to which the ultraviolet ray shielding composition of the present invention is applied include known fiber materials. Examples thereof include polyethylene terephthalate fiber, polyamide fiber, polypropylene fiber, acrylonitrile fiber, polyurethane fiber, polyethylene fiber, polyvinyl chloride fiber, and polyvinylidene chloride fiber. Each processing method is also performed in accordance with a conventionally known spinning method. The addition amount of the ultraviolet shielding composition is preferably about 0.1 to 5 parts by mass with respect to 100 parts by mass of the material as an ultraviolet absorbent residue.

  When applying the ultraviolet shielding composition of the present invention to paper materials, non-woven fabric materials, paints, coating agents, printing agents, printing inks or adhesives, it is done according to a conventionally known method. As the processing method, conventionally known processing methods such as paper making, film formation, coating, printing, and printing are performed. As the paint, conventionally known acrylic melamine type, alkyd melamine type, polyester melamine type, acrylic isocyanate type, aqueous solution type such as two-component polyurethane type, acrylic melamine type, aqueous solution type such as alkyd melamine type, acrylic resin emulsion type, Aqueous dispersion type such as fluororesin emulsion type, powder coating such as acrylic isocyanate type, polyester isocyanate type, polyester epoxy type, etc., UV curing such as urethane acrylate type, epoxy acrylate type, polyester acrylate type, electron beam curable coating type, etc. Is mentioned. Applications include metal plates, especially automobiles, coil coatings, building materials, and woodworking. Similar dry and wet types of coating agents and adhesives can be mentioned.

  Examples of the printing agent to which the ultraviolet shielding composition of the present invention is applied include conventionally known acrylic resin emulsion type, acrylic styrene resin emulsion type, and synthetic rubber type. Printing inks to which the ultraviolet shielding composition of the present invention is applied include conventionally known rotary inks, sheet-fed offset inks, plastic film sheets, gravure inks for aluminum foil, building materials, decorative boards, etc., metal Inks such as board inks can be mentioned. Examples of the electrophotographic developer and inkjet ink to which the ultraviolet shielding composition of the present invention is applied include conventionally known full-color, mono-color, and monochrome dry developers, wet developers, water-based, oil-based, and solid-type inkjet inks. Can be mentioned. In particular, developers and inks used for full color image applications such as advertisements, signboards, and exterior coatings can be mentioned.

  The amount of the ultraviolet shielding composition added to each of the above materials varies depending on the application and purpose of use, but as one criterion, about 0.1 to 10 mass as an ultraviolet absorbent residue with respect to 100 mass parts of resin solid content. It is preferable to add at a ratio of parts. Moreover, a synergistic effect can be acquired by using 2 or more types together including the same kind function or a different function as an ultraviolet-ray shielding composition according to the objective.

  In general, if the product is thin like a thin film such as a film or a fiber, the material is prone to deterioration, or the usage situation is exposed to a harsh environment like an outdoor paint, and it is durable for a long time When the properties are expected, it is desirable to use the ultraviolet shielding composition in a larger ratio as the addition amount.

  Examples of the wet processing method using the ultraviolet shielding composition of the present invention include a heated stirring reaction tank, a mixed stirring reaction tank, and a dissolver mixing. The processing method by wet dispersion includes a mixing roll mill, a kneader, a ball mill, and an attritor. , Sand mills, horizontal media dispersers, vertical media dispersers, continuous horizontal media dispersers, continuous vertical media dispersers, etc. are used. As the dry dissolution and dispersion processing method, the methods and processing machines mentioned in the above resin can be used.

  As pigments used for coloring articles such as the above-mentioned resins, paints, printing agents, printing inks, electrophotographic developers or inkjet inks, organic pigments, inorganic pigments, extender pigments, and dyes that are usually used Is 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, isoindoline pigments, pyrrolopyrrole pigments, fluorescent pigments and other organic pigments, carbon black pigments, titanium oxide pigments, yellow iron oxides, petals, chromium oxides, ultramarine oxides, complex oxide pigments, zinc sulfide, etc. Examples include inorganic pigments, extender pigments such as calcium carbonate, talc, kaolin, and barium sulfate, and further, disperse dyes and oil-soluble dyes, and are not particularly limited.

  In order to improve durability against discoloration, discoloration, etc. of the dye, the ultraviolet ray shielding composition is used in combination, such as coloring composition for resin, paint, printing agent, printing ink, electrophotographic developer or inkjet ink. It is carried out by a method of adding an ultraviolet shielding composition at the time of preparing the composition or a method of preparing a dye processed product by subjecting the pigment to an ultraviolet shielding composition mixing treatment or coating treatment in advance during the production process of the pigment. Depending on the purpose, a plurality of ultraviolet shielding compositions may be used together and processed, and in the case of coating treatment, the ultraviolet shielding composition of the present invention may be processed into a micropolymer bead or immobilized by a crosslinking treatment or the like. Is also effective.

  The polymer-bonded UV absorber used in the UV shielding composition of the present invention is also used in sunscreen products for medicinal cosmetics. In this case, benzoic acid such as benzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, cinnamic acid such as cinnamic acid and p-methoxycinnamic acid, salicylic acid, and acid chlorides thereof. A polymer-bound ultraviolet absorber obtained by condensation reaction of an ultraviolet absorber with the above-described reactive polymer is used in the ultraviolet shielding composition of the present invention. Such an ultraviolet shielding composition of the present invention is highly safe against 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. It can be evenly blended into bases such as creams, milky lotions, oils, lotions, etc., and is less likely to run off in sweat or water baths, and has better stability. The blending amount of the ultraviolet shielding composition is not generally determined depending on the condition of the skin exposure, the purpose of use and the material used, but is used at about 1 to 20% by mass in terms of ultraviolet absorbent residue. The

  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 the text, “part” or “%” is based on mass.

Synthesis Example 1 (Synthesis of polymer-bound UV absorber-1)
In advance, 3- [3 ′-(2 ″ H-benzotriazol-2 ″ -yl) -4′-hydroxyphenyl] propionic acid was reacted with thionyl chloride in a chlorinated solvent according to a conventional method to obtain an acid chloride. Subsequently, 40.0 parts of ethylene-vinyl alcohol copolymer, 500 parts of toluene, and 59.0 of the acid chloride obtained above were put into a reaction vessel equipped with a thermometer, a stirring device and a reflux condenser having a moisture desiccant vessel. The parts were charged, dissolved by heating, and heated to reflux for 5 and a half hours. After allowing to cool, 200 parts of water was added, neutralized with sodium carbonate, poured into isopropyl alcohol to precipitate a reaction product, and filtered. It was thoroughly washed with water and isopropyl alcohol and dried to obtain 82.3 parts of “polymer-bound ultraviolet absorber-1”.

  The product was confirmed by infrared absorption spectrum and NMR. The number average molecular weight by GPC method was about 37,000, and the weight average molecular weight was about 150,000. The content of the ultraviolet absorbent residue in the obtained polymer-bound ultraviolet absorbent-1 is the content in terms of 2- (2 ″ -benzotriazol-2 ″ -yl) -phenol (hereinafter referred to as “BTA”). This is 34%. Further, when a UV-visible absorption spectrum of a solution having a concentration of 100 mg / l in dichloromethane and a diluted solution thereof was measured using a quartz cell, it showed large absorption at 304 nm and 344 nm.

Synthesis Example 2 (Synthesis of polymer-bound ultraviolet absorber-2)
2- {4 "-[(2"'-chlorocarbonyl-propionyloxy) -3 "'-dodecyloxypropyloxy] -2" -hydroxyphenyl} -4,6-bis (2 ', 4'-dimethyl) 78.6 parts of a xylene solution in which 28.6 parts of phenyl) -1,3,5-triazine were dissolved was prepared. In a reaction vessel equipped with a thermometer, a stirrer and a reflux tube, 40.0 parts of the ethylene-vinyl alcohol copolymer used in Synthesis Example 1 was added to 500 parts of xylene and dissolved. Thereto was charged 44.4 parts of the acid chloride used in Synthesis Example 1, dissolved by heating, and heated and stirred at 120 ° C. for 2 hours. Subsequently, the xylene solution of the carboxylic acid chloride of the azine ultraviolet absorber prepared above was added, and the reaction was performed at 130 ° C. for 2 hours. After allowing to cool, 200 parts of isopropyl alcohol and 200 parts of water were added, neutralized with sodium carbonate, poured into isopropyl alcohol to precipitate a reaction product, and filtered. This was thoroughly washed with water and isopropyl alcohol and dried to obtain 93.9 parts of “polymer-bound ultraviolet absorber-2”.

  The product was confirmed by infrared absorption spectrum and NMR. The content of the ultraviolet absorbent residue in the obtained polymer-bound ultraviolet absorbent-2 is 22% in terms of BTA, 2- (2'-hydroxyphenyl) -4,6-bis (phenyl) -1,3, It is 12% in terms of 5-triazine (hereinafter referred to as “TAZ”), and the total converted content is 34%. Polymer-bound UV absorber-2 was dissolved in dichloromethane in the same manner as in Synthesis Example 1, and the UV-visible absorption spectrum was measured. As a result, large absorptions were observed at 299 nm and 342 nm.

Synthesis Example 3 (Synthesis of polymer-bound UV absorber-3)
3- [3 ′-(2 ″ H-benzotriazol-2 ″ -yl) -5′-tbutyl-4′-hydroxyphenyl] propionic acid and ethylene vinyl alcohol copolymer (weight average molecular weight 30,000, ethylene 354 g of 85% content and hydroxyl value 187) were melted together with 200 g of xylene, reacted at 180-230 ° C. for 7 hours under a nitrogen stream, 700 g of xylene was added after completion of the reaction, and then added to 3 L of isopropyl alcohol with stirring. Was precipitated. Subsequently, it filtered and dried and obtained the polymer coupling | bonding ultraviolet absorber-3 (UV absorber residue content 30%). The maximum absorption wavelength of the obtained polymer-bound ultraviolet absorber measured by an optical spectrometer was 305 and 345 nm.

Synthesis Example 4 (Synthesis of polymer-bound ultraviolet absorber-4)
4- [4 '-(2 "H-benzotriazol-2" -yl) -3'-hydroxyphenoxy] butanoic acid from 313 g and ethylene vinyl alcohol copolymer in the same manner as in Synthesis Example 3, polymer-bound UV absorption Agent-4 was obtained. The maximum absorption wavelength of the obtained polymer-bound ultraviolet absorber measured by an optical spectrometer was 340 nm.

Synthesis Example 5 (Synthesis of polymer-bound ultraviolet absorber-5)
From 373 g of 3- [3 ′-(5 ″ -chloro-2 ″ H-benzotriazol-2 ″ -yl) -5′-t-butyl-4′-hydroxyphenyl] propionic acid and an ethylene vinyl alcohol copolymer, Polymer-bonded ultraviolet absorber-5 was obtained in the same manner as in Synthesis Example 3. The maximum absorption wavelength of the obtained polymer-bound ultraviolet absorber measured by an optical spectrometer was 310, 354 nm.

Synthesis Example 6 (Synthesis of polymer-bound ultraviolet absorber-6)
2- [4 '-[(2 "-Carboxypropoxy-3" -dodoxyoxypropyl) oxy] -2'-hydroxyphenyl] -4,6-bis (2', 4'-dimethylphenyl) -1 , 3,5 Triazine and ethylene vinyl alcohol copolymer were used in the same manner as in Synthesis Example 3 to obtain a polymer-bound ultraviolet absorber-6. The maximum absorption wavelength of the obtained polymer-bound ultraviolet absorber measured by an optical spectrometer was 290 and 346 nm.

Example 1 (Production Example of Polymer Bonded UV Absorber Pellets)
The polymer-bound ultraviolet absorber-1 obtained in Synthesis Example 1 is kneaded with a mixing roll (roll surface temperature: 50 ° C.), pulled out as a sheet, and an ultraviolet absorber residue of about 3 × 3 × 2 mm is obtained with a pelletizer. Polymer-bound ultraviolet absorber pellets containing 34% in terms of BTA were used. In the same manner, the polymer-bound ultraviolet absorber-2 obtained in Synthesis Example 2 was drawn out as a sheet and similarly made into a pellet.

Example 2 (Production Example of Masterbatch Containing Polymer Bonded UV Absorber)
After sufficiently mixing 86.1 parts of low-density polyethylene (specific gravity 0.918, MFR: 12) and 13.9 parts of polymer-bound UV absorber-1 with a high-speed mixer (Henschel mixer), a twin-screw extruder is used. The mixture was kneaded and granulated at 130 to 150 ° C. to obtain a master batch containing a columnar polymer-bound ultraviolet absorber-1 having a size of about 3 × 3 mm. This masterbatch contains 5% UV absorber residues. Similarly, the polymer-bonded UV absorber-2 obtained in Synthesis Example 2 was kneaded and granulated with polyethylene to obtain a masterbatch having an equivalent content of UV absorber residue of 5%.

  Similarly, the polymer-bound ultraviolet absorbers -3 to -6 obtained in Synthesis Examples 3 to 6 were added to a polypropylene resin in place of the above polyethylene, kneaded, and granulated, respectively. It was set as the masterbatch whose conversion content rate is 5%.

  Similarly, the polymer-bonded ultraviolet absorber-3 obtained in Synthesis Example 3 was added to a polybutylene terephthalate resin instead of the above polyethylene, kneaded and granulated, and the equivalent content of the ultraviolet absorber residue was 5 % Master batch.

Example 3
0.5% (in the resin) of LLD (linear low density) polyethylene (specific gravity: 0.920, MFR: 2.1) containing the polymer-bound ultraviolet absorber-1 obtained in Example 2 in the resin. 0.1% in terms of BTA equivalent content), and 0.5% of polyethylene masterbatch containing polymer-bound UV absorber-2 (0.1% in terms of total content of TAZ and BTA in the resin) ) And blended with a mixer so that a film with a thickness of 50 μm was obtained with a 30 m / m inflation extruder.

  For comparison, 2- (3′-t-butyl-5′-methyl-2′-hydroxy-phenyl) -2H-5-chloro-benzotriazole (content ratio in terms of BTA: 67%, hereinafter “ 0.15% (referred to as BTA equivalent content in resin: 0.1%) and bis (2,2,6,6-tetramethyl-4-piperidyl (hereinafter referred to as “TMP”) )) Sebacate (content in terms of TMP: 59%, hereinafter referred to as “known light stabilizer-1”) 0.15% (content in terms of TMP in resin: 0.09%) The resultant was added to low density polyethylene, kneaded, and a film having a thickness of 50 μm was obtained using an inflation extruder.

  In order to check the ability of the polyethylene film containing a polymer-bound UV absorber to prevent UV degradation, a weather resistance test was conducted with a weather resistance promotion tester (sunshine type weatherometer, 63 ° C., spray cycle: 12 minutes / hour). The degree of UV degradation of the film was determined by the change in the elongation of the film (tensile speed: 200 mm / min), and compared with a film using a combination of a known UV absorber-1 and a known light stabilizer-1. The measurement results are shown in Table 1.

  As a result, the film without addition of the UV absorber showed significant deterioration over time, particularly the strength at break, whereas the addition of the UV absorber component showed little change and the effect was recognized. . In particular, a film containing a polymer-bonded ultraviolet absorber has a remarkably small decrease in the residual rate of the breaking strength of approximately 10%, indicating that the effect of preventing the deterioration of ultraviolet rays is excellent for a long period of time. A film obtained by adding a light stabilizer to a known ultraviolet absorber showed a 20% decrease in strength at break, indicating a result inferior to that obtained when a polymer-bound ultraviolet absorber was used. This is presumably because the known functional agent added had a low molecular weight, and thus bloomed or volatilized, and the content of the active ingredient was reduced.

Example 4
Low-density polyethylene (specific gravity 0.918, MFR: 12) carbon black pigment masterbatch (pigment content: 30%) 3.3% and polymer-bound UV absorber-1 polyethylene masterbatch of Example 2 Separately, the polyethylene masterbatch containing the polymer-bound ultraviolet absorber-2 is 0.68% in terms of the total content in terms of TAZ and BTA, so that the BTA equivalent content is 0.68%. Mix, knead with a mixing roll (roll surface temperature: 120 ° C.) for 2 minutes, mold with a hot press (160 ° C., 100 kg / cm ² , 1 minute), and contain polymer-bound ultraviolet absorber-1 or -2. Two types of black films of about 0.15 mm were obtained. Similarly, a known ultraviolet absorber-1 was added so as to have a BTA equivalent content of 0.68%, and kneaded and molded to obtain a black film of about 0.15 mm.

  The obtained film was heated in a Kia oven at 60 ° C., and the blooming phenomenon of the ultraviolet absorber on the polyethylene film surface was examined from the state of cloudiness on the surface. The results are shown in Table 2 in comparison with the film containing the known ultraviolet absorber-1. As a result of the blooming test, neither the polyethylene film using the polymer-bound ultraviolet absorber showed any blooming phenomenon on the surface. Films using the known UV absorber-1 caused significant blooming of the UV absorber on the surface.

Example 5
A polypropylene masterbatch containing polypropylene (specific gravity: 0.9, MFR: 7) and the polymer-bound UV absorber-3 obtained in Example 2 was used, and the concentration of the polymer-bound UV absorber-3 was 0.5. %, 1.0%, and 1.5% were blended with a mixer, and a film having a thickness of 50 μm was obtained with a 30 m / m inflation extruder. Similarly, a polypropylene masterbatch containing polypropylene (specific gravity: 0.9, MFR: 7) and the polymer-bonded UV absorbers -4 to 6 obtained in Example 2 is used, and the concentration of the polymer-bonded UV absorber is respectively Blending was performed with a mixer so as to be 0.5%, 1.0%, and 1.5%, and films each having a thickness of 50 μm were obtained with a 30 m / m inflation extruder. For comparison, the concentration of the known ultraviolet absorber-1 in polypropylene (specific gravity: 0.9, MFR: 7) is 0.5%, 1.0%, and 1.5%, respectively. Were blended with a mixer, and films each having a thickness of 50 μm were obtained with a 30 m / m inflation extruder.

  All of the polypropylene films containing the polymer-bound ultraviolet absorbers 3 to 6 had good transparency, and no bleeding of the ultraviolet absorber was observed even after standing for 1 week. On the other hand, bleeding was observed in the polypropylene film containing “known UV absorber-1” having a low molecular weight. The results are shown in Table 3.

Example 6
A polybutylene terephthalate masterbatch containing polyethylene terephthalate (PET) and the polymer-bound ultraviolet absorber-3 obtained in Example 2 was prepared with a polymer-bound ultraviolet absorber-3 concentration of 0.05% and 0.1%, respectively. % And 0.15% were blended with a mixer, and molding plates with a thickness of 1 to 2 mm were obtained with an injection molding machine. Similarly, the polymer-bonded UV absorber-5 was blended with a mixer so that the polymer-bonded UV absorber-5 concentrations were 0.05%, 0.1%, and 0.15%, respectively. Molded plates having a thickness of 1 to 2 mm were obtained with an injection molding machine. All of the obtained molded plates were transparent and no bleed was observed. The results are shown in Table 4.

  In the ultraviolet shielding composition of the present invention, the polymer-bound ultraviolet absorber contained in the composition has good compatibility with the dispersion medium, ultraviolet shielding properties, heat resistance, and bleed resistance. The resulting article is also excellent in transparency, ultraviolet shielding, heat resistance and bleed resistance.

  The ultraviolet shielding composition of the present invention in which the dispersion medium is a resin is, for example, a resin molded product such as a container, film, or sheet, fiber, paper, nonwoven fabric, paint, coating agent, printing agent, printing ink, electrophotographic developer. In the production of inkjet inks, adhesives, cosmetics, etc., it is obtained by adding a polymer-bonded ultraviolet absorber to each raw material resin or solution thereof, vehicle resin or solution or aqueous dispersion thereof by a conventionally known method. . These ultraviolet blocking compositions are each commercialized by conventionally known processing methods or processing methods, for example, molding, spinning, papermaking, etc., and these various products include film formation, coating, textile printing, printing, electrophotographic recording, Used for inkjet printing, adhesion, and the like, and functions such as an improved ultraviolet absorption function are imparted to formed processed articles and recordings.

  As a result, various products are exposed to sunlight, especially reduced in elasticity due to embrittlement of the substrate due to the action of ultraviolet rays, etc., reduced tensile strength, reduced resin physical properties such as cracks, electrical properties, coloring, etc. In addition, it solves problems such as discoloration and discoloration of pigments such as pigments and dyes, and further deteriorates the function due to volatilization of the UV absorber due to evaporation, volatilization, sublimation, etc., which are defects of ordinary low molecular UV absorbers , Limiting the amount added due to compatibility limits, reducing effective amount due to blooming phenomenon on the surface, inhibiting contamination and printability of other articles, adding inorganic UV absorbers to resins (polymer media) Improves the decrease in transparency caused by. Further, in the case of cosmetics, human skin is protected by using the cosmetics.

Claims (9)

A polymer-bound ultraviolet absorber obtained by reacting an ultraviolet absorber having a reactive group with a polymer having a group that reacts with the reactive group,
Benzotriazole-based, triazine-based, benzophenone-based, benzoic acid-based, cinnamic acid-based and salicylic acid having at least one group selected from the group consisting of carboxylic acid alkyl ester group, carboxylic acid halogenide group, hydroxyl group and amino group. At least one selected from the group consisting of UV absorbers of the system,
The polymer is a polymer having at least one group selected from a hydroxyl group, an amino group, a carboxylic acid alkyl ester group and a carboxylic acid halide group,
A UV-shielding composition comprising a polymer-bound UV absorber having a UV absorber residue content of 5 to 95% by mass dispersed in a dispersion medium.   The ultraviolet shielding composition according to claim 1, wherein the dispersion medium is a resin, a resin solution, or an aqueous dispersion medium.   The ultraviolet shielding composition according to claim 2, wherein the resin is a thermoplastic resin or a thermosetting resin.   The ultraviolet shielding composition according to claim 3, wherein the polymer-bound ultraviolet absorber is contained in the resin at a high concentration.   A method for producing an ultraviolet shielding composition, comprising dispersing the polymer-bonded ultraviolet absorber according to claim 1 in a dispersion medium using a kneader, a mixer or a disperser.   A method for producing an ultraviolet shielding resin processed article, comprising molding and processing the ultraviolet shielding composition according to claim 2.   The method for producing an ultraviolet shielding resin processed article according to claim 6, wherein the processed article is a container, a film, a sheet, a pipe, a hose, a tube, a bead, a fiber, an automobile part, an electric equipment part, a stationery, furniture, or daily necessities.   A method for producing an ultraviolet shielding processed article, comprising applying the ultraviolet shielding composition according to claim 2 or 3 to a substrate by a coating method, an impregnation method, or a printing method.   An ultraviolet shielding processed article obtained by the production method according to claim 8.