Resin composition, and molded body

Abstract

To provide a resin composition which enables molding of a molded body that has heat resistance to withstand melting and kneading at 270°C or higher, absorbs not only ultraviolet light of less than 400 nm but also light of a visible light short wavelength region of approximately 400 to 420 nm, and has good transparency.SOLUTION: A resin composition for molding is a resin composition for molding (excluding application of a fiber), which absorbs light in an ultraviolet region of less than 400 nm and a visible light short wavelength region of 400 to 420 nm and is a molten and kneaded material of an ultraviolet absorption dye (A) and a thermoplastic resin (B). The resin composition contains 0.001 to 5 mass% of the ultraviolet absorption dye (A), and the thermoplastic resin (B) is a crystalline resin having a melting point of 200 or more or an amorphous resin having a glass transition temperature of 120 or more.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition and a molded article containing an ultraviolet absorber.

Background Art

[0002] Conventionally, resin molded articles (hereinafter referred to as molded articles) have been used as packaging materials for pharmaceutical agents, cosmetics, etc. It is known that the organic substances inside these packaging materials generally deteriorate due to the action of ultraviolet rays contained in sunlight or the like.

[0003] It has been pointed out that not only ultraviolet rays of less than 400 nm but also light in the short-wavelength visible light region of about 400 to 420 nm in sunlight can damage organic substances and the human body. Therefore, containing an ultraviolet absorber that absorbs ultraviolet rays and light in the short-wavelength visible light region of about 400 to 420 nm in the molded article is effective in suppressing the deterioration of the contents. Furthermore, an ultraviolet absorber with excellent light resistance that does not deteriorate its properties due to long-term exposure to ultraviolet rays is required.

[0004] As uses of molded articles other than packaging materials, optical uses can be mentioned, for example, a polarizing plate protection film used in a liquid crystal display device, an antireflection film, a surface film for preventing deterioration of a light-emitting element of an organic EL display device, etc.

[0005] In these optical uses, there is a high-temperature processing process, while high dimensional stability is required. In particular, molded articles using engineering plastics have a high molding processing temperature, for example, 260 to 340°C, so the ultraviolet absorber requires heat resistance that can withstand high temperatures.

[0006] Patent Documents 1 to 2 disclose benzotriazole-based ultraviolet absorbers that absorb the short-wavelength visible light region of about 400 to 420 nm.

Prior Art Documents

Patent Documents

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2018-177696 [Patent Document 2] Japanese Patent Application Publication No. 2016-514756 [Summary of the Invention] [Problems to be Solved by the Invention]

[0008] However, conventional resin compositions have a problem that the heat resistance of the ultraviolet absorber is low and they cannot be used for molded articles of thermoplastic resins (for example, engineering plastics) having a high melting point or a high softening point. Also, in order to absorb light in the short-wavelength visible light region of about 400 to 420 nm, the extinction coefficient per unit weight is low, and it is necessary to increase the thickness of the molded article, so there is a problem that it cannot be made into a thin film. On the other hand, there is also a problem that the transparency of the molded article decreases when the amount of the ultraviolet absorber is increased.

[0009] An object of the present invention is to provide a resin composition capable of molding a molded article having heat resistance that can withstand melt kneading at 270 ° C. or higher, absorbing not only ultraviolet light of less than 400 nm but also light in the short-wavelength visible light region of about 400 to 420 nm, and having good transparency. [Means for Solving the Problems]

[0010] The resin composition of the present invention is a resin composition that is a melt kneaded product of an ultraviolet absorbing dye (A) that is a triazine compound that absorbs light in the ultraviolet region of less than 400 nm and the short-wavelength visible light region of 400 to 420 nm and binds to one, two, or three naphthalene rings, and a thermoplastic resin (B), and the thermoplastic resin (B) is a crystalline resin having a melting point of 200 ° C. or higher or an amorphous resin having a glass transition temperature of 120 ° C. or higher. [Effects of the Invention]

[0011] ​According to the present invention described above, it is possible to provide a resin composition capable of forming a molded article having heat resistance that can withstand melt kneading at 270 °C or higher, absorbing not only ultraviolet light of less than 400 nm but also light in the short wavelength region of visible light of about 400 to 420 nm, and having good transparency, and a molded article.

Mode for Carrying Out the Invention

[0012] The resin composition of the present invention is a resin composition that is a melt kneaded product of an ultraviolet absorbing dye (A) that is a triazine compound that absorbs light in the ultraviolet region of less than 400 nm and the short wavelength region of visible light of 400 to 420 nm, and a thermoplastic resin (B), and the thermoplastic resin (B) is a crystalline resin having a melting point of 200 °C or higher or an amorphous resin having a glass transition temperature of 120 °C or higher.

[0013] The ultraviolet absorbing dye (A) contained in the resin composition of the present invention can absorb light in the short wavelength region of visible light of about 400 to 420 nm in addition to the ultraviolet region of less than 400 nm due to the action of the naphthalene ring bonded to the triazine ring. Further, the ultraviolet absorbing dye (A) of the present invention has an unexpected effect that desired wavelength absorption can be achieved with a smaller amount of addition than in the past. In addition, since wavelength absorption is possible with a small amount, the amount of addition can be suppressed, and thus it has an effect of improving the transparency without reducing the transparency of the molded article. Note that the naphthalene ring is preferably directly bonded to the triazine ring without a linking group. Further, it is more preferable that at least one of the 1 to 3 naphthalene rings directly bonded to the triazine contains a hydroxyl group at the 2-position.

[0014] As the ultraviolet absorbing dye (A) contained in the resin composition of the present invention, a compound selected from the group consisting of the following general formula (1), general formula (2), and general formula (3) is preferable.

Chemical formula

[0015] (In general formulas (1) to (3), R 1b ~R 1g 、R 2a ~R2g , R 3a ~R 3g are each independently a hydrogen atom, a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitrile group, a nitro group, a sulfo group, R7, Ar1, or a group represented by the following general formulas (4-1) to (4-3). R7 is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkenyloxy group having 1 to 20 carbon atoms, and may have a substituent of a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitrile group, a nitro group, a carboxyl group, or a sulfo group, and the carbon atoms of the alkyl group having 1 to 20 carbon atoms, the alkenyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms, or the alkenyloxy group having 1 to 20 carbon atoms may be linked by one or more -O-, -CO-, -COO-, -OCO-, -CONH-, or -NHCO-. Ar1 is an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or a biphenyl group, and may have a substituent of a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitrile group, a nitro group, a carboxyl group, or a sulfo group. In general formulas (2) to (3), R4, R5, and R6 are a hydroxyl group, R7, or Ar1. General formula (4-1)

Chemical formula

[0016] In general formula (4-1), X1 is -CO-, -COO-, -OCO-, -CONH-, or -NHCO-. R8 is a hydrogen atom, a hydroxyl group, R7, or Ar1. However, * in general formula (4-1) represents the bonding site with the naphthalene ring of general formulas (1) to (3). General formula (4-2)

Chemical formula

[0017] In general formula (4-2), X2 and X3 are each independently -CO-, -COO-, -OCO- , -CONH-, or -NHCO-. R9 is an arylene group having 6 to 20 carbon atoms. R 10 is R7 or Ar1. However, * in general formula (4-2) represents the bonding site with the naphthalene ring of general formulas (1) to (3). General formula (4-3)

Chemical formula

[0018] In general formula (4-3), X4 and X5 are each independently -CO-, -COO-, -OCO-, -CONH-, or -NHCO-. R 11 is a linear or branched alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. R 12 is R7 or Ar1. n is 1 to 20. However, * in general formula (4-3) represents the bonding site with the naphthalene ring of general formulas (1) to (3).)

[0019] Note that the group represented by general formula (4-1) is preferably the group represented by general formula (4). General formula (4)

Chemical formula

[0020] In general formula (4), Y is -NH- or -O-. R 13is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, which may have a substituent such as a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitrile group, a nitro group, a carboxyl group, or a sulfo group. However, the * mark in the general formula (4) represents the bonding site with the naphthalene ring in the general formulas (1) to (3).

[0021] Examples of the compound represented by the general formula (1) include the following compounds. [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula]

[0022] Examples of the compound represented by the general formula (2) include the following compounds. [Chemical formula]

[0023] Examples of the compound represented by the general formula (3) include the following compounds. [Chemical formula]

[0024] The synthesis method of the above triazine compound can be carried out using a known synthesis method of a compound having a triazine structure. For example, a method of adding naphthol or a naphthol derivative to cyanuric chloride using aluminum trichloride can be mentioned. Additionally, for example, a method of subjecting methyl 2-hydroxy-1-naphthoate and benzamidine hydrochloride to a condensation cyclization reaction using sodium methoxide can also be mentioned. The naphthalene ring and the substituents of R4, R5, and R6 linked to the triazine ring by a single bond may be introduced after the formation of the triazine structure or before the formation of the triazine structure.

[0025] The content of the ultraviolet absorber (A) is preferably 0.001 to 5% by mass, more preferably 0.005 to 1% by mass in 100% by mass of the resin composition.

[0026] <(Thermoplastic resin (B))> The thermoplastic resin (B) is a crystalline resin having a melting point of 200°C or higher or an amorphous resin having a glass transition temperature of 120°C or higher. The melting point of the crystalline resin is preferably 220°C or higher. Also, the melting point is preferably 500°C or lower. The glass transition temperature of the amorphous resin is preferably 130°C or higher. Also, the glass transition temperature is preferably 300°C or lower. Both the melting point and the glass transition temperature can be measured using a differential scanning calorimeter, a thermogravimetric differential thermal analyzer, or the like.

[0027] Examples of the crystalline resin having a melting point of 200°C or higher include polyester resins, polyamide resins, polyacetal resins, polyphenylene sulfide resins, polyether ether ketone resins, and the like. Examples of the amorphous resin having a glass transition temperature of 120°C or higher include cycloolefin resins, polyetherimide resins, polyamideimide resins, polyethersulfone resins, polysulfone resins, polyarylate resins, polyphenylene ether resins, polycarbonate resins, and the like.

[0028] <(Polyester resin)> Polyester is a crystalline resin having an ester bond in the main chain of the molecule and a dicarboxylic acid A polycondensate synthesized from (including its derivatives), and a diol (dihydric alcohol or dihydric phenol); a polycondensate synthesized from a dicarboxylic acid (including its derivatives) and a cyclic ether compound; a ring-opening polymer of a cyclic ether compound, etc. are mentioned. Polyester includes a homopolymer made of a polymer of a dicarboxylic acid and a diol, a copolymer using a plurality of raw materials, and a polymer blend obtained by mixing these. Note that the derivative of the dicarboxylic acid is an acid anhydride or an esterified product. There are two types of dicarboxylic acids, aliphatic and aromatic, and aromatic ones that improve heat resistance are more preferable.

[0029] Aromatic dicarboxylic acids include, for example, terephthalic acid, isophthalic acid, phthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, diphenyldiacetic acid, diphenyl-p,p'-dicarboxylic acid, diphenyl-4,4'-diacetic acid, diphenylmethane-p,p'-dicarboxylic acid, diphenylethane-m,m'-dicarboxylic acid, stilbenylcarboxylic acid, diphenylbutane-p,p'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, p-carboxyphenoxyacetic acid, p-carboxyphenoxybutyric acid, 1,2-diphenoxypropane-p,p'-dicarboxylic acid, 1,5-diphenoxypentane-p,p'-dicarboxylic acid, 1,6-diphenoxyhexane-p,p'-dicarboxylic acid, p-(p-carboxyphenoxy)benzoic acid, 1,2-bis(2-methoxyphenoxy)-ethane-p,p'-dicarboxylic acid, 1,3-bis(2-methoxyphenoxy)propane-p,p'-dicarboxylic acid, 1,4-bis(2-methoxyphenoxy)butane-p,p'-dicarboxylic acid, 1,5-bis(2-methoxyphenoxy)-3-oxypentane-p,p'-dicarboxylic acid, etc. Aliphatic dicarboxylic acids include, for example, oxalic acid, succinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, undecanedicarboxylic acid, maleic acid, fumaric acid, and the like.

[0030] Dihydric alcohols include, for example, ethylene glycol, trimethylene glycol, butane-1,3-diol, butane-1,4-diol, 2,2-dimethylpropane-1,4-diol, cis-2-butene-1,4-diol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, cyclohexanedimethanol, and the like. Among these, ethylene glycol, butane-1,4-diol, and cyclohexanedimethanol are preferred. Diphenols include, for example, hydroquinone, resorcinol, bisphenol A, and the like. Cyclic ether compounds include, for example, ethylene oxide, propylene oxide, and the like.

[0031] The dicarboxylic acids and dihydric alcohols can be used alone or in combination of two or more thereof.

[0032] <Polyamide resin> The polyamide resin is a crystalline resin and can be synthesized, for example, by subjecting a carboxylic acid component and a compound (Am) having two or more amino groups to a dehydration condensation reaction.

[0033] The carboxylic acid component includes, for example, adipic acid, sebacic acid, isophthalic acid, terephthalic acid, and the like. Note that a compound having three or more carboxyl groups can be used as the carboxylic acid component. As the compound (Am) having two or more amino groups, for example, known ones can be used, such as ethylenediamine, propylenediamine, trimethylenediamine, tetra Aliphatic polyamines such as ethylenediamine, pentamethylenediamine, hexamethylenediamine, and triethylenetetramine; alicyclic polyamines containing alicyclic polyamines such as isophoronediamine and dicyclohexylmethane-4,4'-diamine; aromatic polyamines such as phenylenediamine and xylylenediamine; and diaminoalcohols such as 1,3-diamino-2-propanol, 1,4-diamino-2-butanol, 1-amino-3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-ol, 4-(2-aminoethyl)-4,7,10-triazadecane-2-ol, and 3-(2-hydroxypropyl)-o-xylene-α,α'-diamine. Commercially available polyamide resins include, for example, 6 nylon (manufactured by Toray Industries, Inc.), 66 nylon (manufactured by Toray Industries, Inc.), 610 nylon, and the like.

[0034] <Cycloolefin resin> Cycloolefin resin is an amorphous resin having an alicyclic structure in the main chain and / or side chain. Examples of the types of alicyclic structures include, for example, norbornene polymers, monocyclic cyclic olefin polymers, cyclic conjugated diene polymers, and vinyl alicyclic hydrocarbon polymers, and hydrides thereof. Among these, norbornene polymers are preferred because of their excellent moldability and transparency. Examples of norbornene monomers include, for example, bicyclo[2.2.1]hept-2-ene (common name: norbornene), tricyclo[4.3.0.12,5]deca-3,7-diene (common name: dicyclopentadiene), 7,8-benzotricyclo[4.3.0.12,5]deca-3-ene (common name: methanotetrahydrofluorene), tetracyclo[4.4.0.12,5.17,10]dodeca-3-ene (common name: tetracyclododecene), and the like. Commercially available cycloolefin resins include, for example, Topas (manufactured by Polyplastics Co., Ltd.) and Apel (manufactured by Mitsui Chemicals, Inc.).

[0035] <Polyetherimide resin> The polyetherimide resin is an amorphous resin with a glass transition temperature exceeding 180°C, having good transparency, high strength, high heat resistance, high elastic modulus, and a wide range of chemical resistance. Therefore, it is widely used in various applications such as automobiles, telecommunications, aerospace, electrical / electronics, transportation, and healthcare. One of the manufacturing processes of polyetherimide resin is by the polymerization of an alkali metal salt of a dihydroxy aromatic compound such as sodium bisphenol A (BPA·Na2) and bis(halophthalimide). The molecular weight of the obtained polyetherimide resin can be controlled by two methods. The first method is to use a molar excess of bis(halophthalimide) with respect to the alkali metal salt of the dihydroxy aromatic compound. The second method is to prepare bis(anhydrohalophthalic acid) in the presence of a monofunctional compound such as phthalic anhydride that forms a terminal capping agent. Phthalic anhydride reacts with a part of the organic diamine to form monohalo-bis(phthalimide). Monohalo-bis(phthalimide) acts as a terminal capping agent in the polymerization step by reaction with the phenoxide end groups in the growing polymer chain. Commercially available polyetherimide resins include ULTEM (manufactured by Saudi Basic Industries Corporation).

[0036] <Polycarbonate resin> The polycarbonate resin is an amorphous resin, which is synthesized by reacting an aromatic dihydroxy compound with a carbonate precursor such as phosgene or a carbonic acid diester. In the case of the synthesis reaction using phosgene, for example, the interfacial method is preferred. In the case of the synthesis reaction using a carbonic acid diester, the transesterification method of reacting in a molten state is preferred.

[0037] The aromatic dihydroxy compound is, for example, 2,2-bis(4-hydroxyphenyl Bis(hydroxyaryl)alkanes such as bisphenol A, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-t-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane; bis(hydroxyaryl)cycloalkanes such as 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane; dihydroxydiarylethers such as 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether; dihydroxydiarylsulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; dihydroxydiarylsulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; dihydroxydiarylsulfones such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, etc. Also, piperazine, dipiperidylhydroquinone, resorcinol, 4,4'-dihydroxydiphenyls may be used in combination.

[0038] Examples of the carbonate precursor include diaryl carbonates such as phosgene, diphenyl carbonate, ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, etc.

[0039] The viscosity average molecular weight of the polycarbonate resin is preferably from 15,000 to 30,000, more preferably from 16,000 to 27,000. The viscosity average molecular weight in this specification is a value converted from the solution viscosity measured at a temperature of 25 ° C using methylene chloride as a solvent.

[0040] Commercially available polycarbonate resins include, for example, Iupilon H-4000 (manufactured by Mitsubishi Engineering Plastics Corporation, viscosity average molecular weight 16,000), Iupilon S-3000 (manufactured by Mitsubishi Engineering Plastics Corporation, viscosity average molecular weight 23,000), Iupilon E-2000 (manufactured by Mitsubishi Engineering Plastics Corporation, viscosity average molecular weight 27,000), and the like.

[0041] When the thermoplastic resin (B) has an appropriate melt flow rate (MFR), high fluidity and moldability can be achieved simultaneously. The MFR of each resin can be measured according to Japanese Industrial Standard JIS K 7210 and is preferably in the following range.

[0042] The MFR of the thermoplastic resin (B) varies depending on the resin type, but is preferably 1 to 200 g / 10 min, more preferably 2 to 150 g / 10 min, and even more preferably 5 to 100 g / 10 min at a temperature (about 200 to 320 ° C) exceeding the melting point or glass transition temperature. Hereinafter, the preferred MFR for each resin will be described.

[0043] The MFR of the polyester resin is preferably 1 to 200 g / 10 min, more preferably 5 to 150 g / 10 min, and even more preferably 10 to 150 g / 10 min at 280 ° C / 2.16 kg.

[0044] The MFR of the polycarbonate resin is preferably 1 to 100 g / 10 min, more preferably 2 to 80 g / 10 min, and even more preferably 2 to 50 g / 10 min at 300 ° C / 1.2 kg.

[0045] The MFR of the cycloolefin resin is preferably 1 to 100 g / 10 min, more preferably 2 to 80 g / 10 min, and even more preferably 5 to 60 g / 10 min at 260 °C / 2.16 kg.

[0046] The MFR of the polyamide resin is preferably 1 to 100 g / 10 min, more preferably 2 to 80 g / 10 min, and even more preferably 5 to 80 g / 10 min at 235 °C / 2.16 kg.

[0047] The MFR of the polyetherimide resin is preferably 1 to 100 g / 10 min, more preferably 2 to 80 g / 10 min, and even more preferably 3 to 50 g / 10 min at 337 °C / 6.6 kg.

[0048] The resin composition of the present invention can contain additives in addition to the ultraviolet absorbing dye (A) and the thermoplastic resin (B). Examples of the additives include near-infrared absorbers, light stabilizers, antioxidants, colorants, waxes, and the like. Compounds known in the art for use in molded article applications can be used for these additives.

[0049] The near-infrared absorber is used to impart near-infrared absorption ability to the molded article. Examples of the near-infrared absorber include compounds such as cyanine-based, diimonium-based, squarylium-based, and phthalocyanine-based compounds. The content of the near-infrared absorber is preferably 0.01 to 5% by mass in 100% by mass of the resin composition.

[0050] The light stabilizer is used to impart ultraviolet resistance to the molded article. The light stabilizer is preferably, for example, a hindered amine light stabilizer. The content of the light stabilizer is preferably 0.01 to 5% by mass in 100% by mass of the resin composition.

[0051] The antioxidant is used to reduce the deterioration of the molded article when the molded article is exposed to natural light or an artificial light source and becomes hot. The antioxidant is preferably, for example, monophenol-based, bisphenol-based, polymer-type phenol-based, sulfur-based, phosphoric acid-based, etc. The content of the antioxidant is preferably 0.01 to 5% by mass in 100% by mass of the resin composition.

[0052] The wax is used to more uniformly disperse the ultraviolet absorber dye in the molded article. As the dispersant, for example, polyolefin wax, fatty acid wax, fatty acid ester wax, partially saponified fatty acid ester wax, saponified fatty acid wax, etc. are preferable. The content of the wax is preferably 50 to 250 parts by mass with respect to 100 parts by mass of the ultraviolet absorber dye (A).

[0053] <Preparation of resin composition> The method for producing the resin composition of this specification is a method for producing a resin composition in which an ultraviolet absorber dye (A) which is a compound selected from the group consisting of general formula (1), general formula (2) and general formula (3), and a thermoplastic resin (B) are melt-kneaded. The thermoplastic resin (B) is a crystalline resin having a melting point of 200°C or higher, or an amorphous resin having a glass transition temperature of 120°C or higher. It is preferable to cool the resin composition after melt-kneading.

[0054] The melt-kneading temperature is preferably 270°C or higher, more preferably 300°C or higher. In particular, resins such as engineering plastics with high heat resistance have low fluidity, so a processing process at a high temperature is preferable. The upper limit of the melt-kneading temperature is not limited because it varies depending on the type of the thermoplastic resin (B). The upper limit is preferably 500°C or lower, more preferably 450°C or lower if forced to mention. Also, the upper limit needs to be less than the sublimation temperature or the decomposition temperature of the ultraviolet absorber dye (A). less than.

[0055] Examples of the melt-kneading device include a single-screw kneading extruder, a twin-screw kneading extruder, a tandem twin-screw kneading extruder, etc.

[0056] The resin composition is preferably prepared as a so-called masterbatch. When the masterbatch is prepared and then melt-kneaded with a diluent resin (thermoplastic resin (B)) to produce a molded article, the ultraviolet-absorbing dye (A) is more easily dispersed uniformly in the molded article and aggregation of the ultraviolet-absorbing dye (A) can be suppressed as compared with a molded article produced without passing through the masterbatch. Thereby, the transparency of the molded article is improved. The masterbatch is preferably formed into pellets using a pelletizer after the melt-kneading. When prepared as a masterbatch, the content of the ultraviolet-absorbing dye (A) is preferably 0.01 to 20% by mass, more preferably 0.05 to 2% by mass in 100% by mass of the resin composition.

[0057] <Liquid masterbatch (F)> It is more preferable to prepare a liquid masterbatch (F) containing an ultraviolet-absorbing dye (A) and a liquid resin (E), and then melt-knead it with a diluent resin (thermoplastic resin (B)) to produce the resin composition.

[0058] (Liquid resin (E)) The liquid resin (E) functions as a dispersion medium for dispersing the ultraviolet-absorbing dye (A). The liquid resin (E) is a resin having a viscosity at 25°C of 10,000 mPa·s or less. The viscosity is more preferably 10 to 5,000 mPa·s, and even more preferably 100 to 3,000 mPa·s. When within the above range, the ultraviolet-absorbing dye (A) can be easily dispersed in the liquid masterbatch. The viscosity in this specification is a value measured at 25°C using a B-type viscometer in accordance with JIS K7117-1:1999.

[0059] The content of the liquid resin (E) is preferably 50% by mass or more, more preferably 60 to 95% by mass, and even more preferably 70 to 90% by mass in 100% by mass of the liquid masterbatch (F). By being within this range, for example, during melt-kneading, the melt viscosity can be suppressed, making it easier to disperse the ultraviolet-absorbing dye (A).

[0060] The number average molecular weight (Mn) of the liquid resin (E) is preferably from 200 to 2000, more preferably from 500 to 1500, and particularly preferably from 1000 to 1500. When Mn is 200 or more, it is easy to achieve both moldability and transparency. Also, when Mn is 2000 or less, dispersibility and antistatic properties are improved.

[0061] Examples of the liquid resin (E) include epoxy resins such as epoxidized soybean oil and epoxidized linseed oil, fatty acid polyester resins, polyalkylene glycol resins, polyether resins, or polyether ester resins. However, when the thermoplastic resin (B) requires a high molding temperature such as polyethylene terephthalate (PET) or polycarbonate, fatty acid polyester resins, polyalkylene glycol resins, or polyether ester resins are preferred in terms of high heat resistance and excellent antistatic properties.

[0062] [Fatty acid polyester resin] It is a resin obtained by the reaction of an aliphatic polycarboxylic acid and a polyhydric alcohol. The aliphatic polycarboxylic acid is an aliphatic carboxylic acid having two or more carboxyl groups. Examples of the aliphatic polycarboxylic acid include aliphatic polycarboxylic acids such as succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, tricarballylic acid, 1,3,6 - hexanetricarboxylic acid, and 1,3,5 - hexanetricarboxylic acid.

[0063] The polyhydric alcohol is an alcohol having two or more hydroxyl groups. Examples of the polyhydric alcohol include aliphatic glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, and polyalkylene glycols such as diethylene glycol and dipropylene glycol.

[0064] The aliphatic polycarboxylic acid and the polyhydric alcohol can be used alone or in combination of two or more.

[0065] The freezing point of the fatty acid polyester resin is preferably -5°C or lower, more preferably -50°C to -10°C.

[0066] Examples of commercially available fatty acid polyester resins include Adeka Sizer PN-170 (manufactured by ADEKA, viscosity at 25°C: 800 mPa·s, freezing point: -15°C, adipic acid polyester resin), Adeka Sizer P-200 (manufactured by ADEKA, viscosity at 25°C: 2,600 mPa·s, freezing point: -20°C, adipic acid polyester resin), Adeka Sizer PN-250 (manufactured by ADEKA, viscosity at 25°C: 4,500 mPa·s, freezing point: -20°C, adipic acid polyester resin), and the like.

[0067] [Polyether resin] The polyether resin is a resin having a repeating unit of an alkyleneoxy group. The number of carbon atoms in the alkyleneoxy group is preferably 1 to 6. The polyether resin preferably has a viscosity at 25°C of 10,000 mPa·s or less. With this viscosity, it is suitable for use in liquid masterbatch applications. Incidentally, the number of carbon atoms in the alkyleneoxy group is preferably 2 to 4. Thereby, while the compatibility is improved, the water absorption can be suppressed.

[0068] Examples of the polyether resin include polyethylene glycol in which the number of carbon atoms in the repeating unit is 2, polytrimethylene glycol and polypropylene glycol in which the number of carbon atoms in the repeating unit is 3, and polytetramethylene glycol and polybutylene glycol in which the number of carbon atoms in the repeating unit is 4.

[0069] [Polyether ester resin] The polyether ester resin is an ester compound of an aliphatic polyvalent carboxylic acid resin and an alkylene glycol resin. Examples of commercially available polyether ester resins include Adeka Sizer RS-107 (manufactured by ADEKA, viscosity at 25°C: 20 mPa·s, freezing point: -47°C, adipic acid ether ester resin), Adeka Sizer RS-700 (manufactured by ADEKA, viscosity at 25°C: 30 mPa·s, freezing point: -53°C, polyether ester resin), and the like.

[0070] The freezing point of the liquid resin (E) is preferably -5°C or lower, more preferably -50°C to -10°C.

[0071] The resin composition of the present invention is prepared by producing a liquid masterbatch (F) and then melt-kneading it together with a diluent resin (thermoplastic resin (B)). The molded article produced using this has better transparency than the molded article produced from a conventional solid masterbatch.

[0072] Since the liquid masterbatch (F) contains the liquid resin (E) and is in a liquid state, it has high fluidity in the melt-kneading with the thermoplastic resin (B) and can disperse the ultraviolet-absorbing dye (A) very uniformly. In particular, resins of engineering plastics with high heat resistance have limitations in fluidity even at the melt-kneading temperature. Therefore, it is difficult to achieve uniform dispersion due to the aggregation of the dye, and it is difficult to improve transparency. Thus, in the case of the thermoplastic resin (B) which is a crystalline resin with a melting point of 200 °C or higher or an amorphous resin with a glass transition temperature of 120 °C or higher, the liquid masterbatch (F) is effective in improving transparency. In particular, it is particularly effective in applications that require high transparency such as optical filters.

[0073] The content of the ultraviolet-absorbing dye (A) in the liquid masterbatch (F) is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, in 100% by mass of the liquid masterbatch.

[0074] (Resin type dispersant (G)) The liquid masterbatch (F) preferably contains a resin type dispersant (G). Thereby, in the liquid masterbatch, the ultraviolet-absorbing dye (A) is more uniformly dispersed, and the resulting molded article can obtain higher transparency. Further, by including the resin type dispersant (G), the storage stability of the liquid masterbatch is improved.

[0075] The resin type dispersant (G) is a compound having an adsorption site having a property of adsorbing to the ultraviolet-absorbing dye and a relaxation site compatible with components other than the ultraviolet-absorbing dye. The resin-based dispersant (G) includes, for example, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, oil-based dispersants such as amides and their salts formed by the reaction of poly(lower alkyleneimine) and a polyester having a free carboxyl group, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate copolymers, styrene-maleic acid copolymers, water-soluble resins and water-soluble polymer compounds such as polyvinyl alcohol and polyvinyl pyrrolidone, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide addition compounds, phosphate ester-based, and the like.

[0076] The resin-based dispersant (G) can be used alone or in combination of two or more.

[0077] Among the above resin-based dispersants, polymer dispersants having basic functional groups are preferred because the viscosity of the dispersion becomes low with a small addition amount. Further, nitrogen atom-containing graft copolymers, nitrogen atom-containing acrylic block copolymers and urethane-based polymer dispersants having functional groups containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocyclic ring, etc. in the side chain are preferred.

[0078] The usage amount of the resin-based dispersant (G) is preferably about 5 to 200% by mass, more preferably about 10 to 100% by mass, based on the ultraviolet absorbing dye (A), from the viewpoint of film-forming property.

[0079] Commercially available resin-based dispersants include, for example, DisperbYk- manufactured by BYK-Chemie Japan 101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or BYkumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. manufactured by Lubrizol Japan Co., Ltd., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. manufactured by Chiba Japan Co., Ltd., Ajisper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Inc. may be mentioned.

[0080] In addition, when the resin-type dispersant (G) is in a state dissolved in an organic solvent, it is preferable to add the liquid resin (E), heat under reduced pressure, and distill off the solvent for use.

[0081] <Method for manufacturing the liquid masterbatch (F)> Liquid masterbatch (F) can be prepared by mixing and dispersing an ultraviolet-absorbing dye (A) and a liquid resin (E). In addition, a resin-type dispersant (G) can be used in combination for the dispersion. For the dispersion, for example, a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or a attritor and other dispersing devices can be used.

[0082] The molded article of this specification is preferably produced by molding a resin composition. The resin composition can be directly molded to produce a molded article. Further, when the resin composition is adjusted as a masterbatch, it can be melt-kneaded together with a diluent resin (thermoplastic resin (B)) and then molded to produce a molded article. The mass ratio of masterbatch (X) to diluent resin (Y) is preferably X / Y = 1 / 5 to 1 / 500. When in this range, the molded product is likely to obtain good optical properties.

[0083] When using liquid masterbatch (F) as the masterbatch, it is more preferable to contain 0.1 to 5% by mass of liquid masterbatch (F) in 100% by mass of the resin composition.

[0084] <Use> The composition of the present invention can be used, for example, in food packaging materials, pharmaceutical packaging materials, displays, interlayer films for glass, and lens applications.

[0085] For food packaging materials and pharmaceutical packaging materials, it is preferable to use, for example, polyester resins, cycloolefin resins, etc. in thermoplastic resins. These molded articles have improved flexibility and visibility and can suppress the deterioration of the contents.

[0086] The molded article used for display, glass interlayer, and lens applications may be any molded article composed of a thermoplastic resin, but is preferably a film made of a resin having a property of being transparent to a desired wavelength. Examples of the resin constituting such a molded article include polyetherimide resin, polyethersulfone resin, polyethylene terephthalate resin, polyimide resin, polysulfone resin, polyarylate resin, polyamide resin, polycarbonate resin, olefin polymer resin having an alicyclic structure (alicyclic olefin polymer resin), cellulose ester resin, and the like.

[0087] In display applications, for example, it is used in optical films such as those used in televisions, personal computers, smartphones, etc. The laminate using the molded article containing the above composition can suppress the adverse effects on the eyes by absorbing the light in the short wavelength region of ultraviolet rays and visible light contained in the backlight of the display, and can also suppress the deterioration of the display element by absorbing the light in the short wavelength region of ultraviolet rays and visible light contained in sunlight.

[0088] In glass interlayer applications, for example, it is used in laminated glass such as those used in automobiles and buildings. The laminated glass using the molded article containing the above composition can suppress the adverse effects on the eyes and the human body by absorbing the light in the short wavelength region of ultraviolet rays and visible light contained in sunlight.

[0089] In lens applications, for example, it is used in lenses such as those used in glasses and optical sensors. The lens using the molded article containing the above composition can suppress the adverse effects on the eyes and the human body by absorbing the light in the short wavelength region of ultraviolet rays and visible light contained in sunlight in the case of glasses applications, and can enhance the sensitivity of the sensor by cutting off the light of unnecessary wavelengths that can become noise in optical sensor applications.

[0090] The molded articles described in this specification can be widely used in applications such as medical drugs, cosmetics, food containers and packaging materials, sundries, textile products, pharmaceutical containers, various industrial coating materials, automotive parts, household appliances, building materials for houses, etc., and toiletries. Furthermore, they can also be widely used in applications such as display materials, sensor materials, and optical control materials.

Examples

[0091] Hereinafter, the present invention will be described in more detail. Note that the present invention is not limited to the examples. Also, "parts by mass" will be described as "parts", and "mass%" will be described as "%".

[0092] <Method for Producing Ultraviolet Absorbing Dye (A)> [Ultraviolet Absorbing Dye (A-1)] 170 parts of chlorobenzene, 43.4 mmol of cyanuric chloride, and 65.1 mmol of aluminum chloride were charged into a 300 mL Erlenmeyer flask and stirred to form a suspension. Next, 151.8 mmol of 2-naphthol was added little by little while cooling with ice water. Then, it was stirred overnight while gradually returning to room temperature. On the other hand, 38.1 parts of water, 10.0 parts of 35% hydrochloric acid, and 45.0 parts of methanol were charged into a 500 mL beaker, and the previous reaction solution was added dropwise little by little. Further, 45.0 parts of methanol was added to the Erlenmeyer flask in multiple portions and added to the 500 mL beaker while washing. The precipitate was filtered off and washed by sprinkling with a mixed solvent of water / methanol = 75 parts / 75 parts. The obtained wet cake was returned to 150 parts of water and slurried at room temperature for 30 minutes, then filtered off. Thereafter, it was washed by sprinkling with 150 parts of water. The obtained wet cake was dried at 80 °C overnight to obtain ultraviolet absorbing dye (A-1).

[0093] As a result of performing NMR measurement on the ultraviolet absorbing dye (A-1), results supporting the above structure were obtained. The measurement conditions are as follows. <Measurement Conditions> Apparatus: BRUKER AVANCE400 Resonance frequency: 400 MHz (1H-NMR) Solvent: Dimethyl sulfoxide-d8 Tetramethylsilane was used as the internal standard substance for 1H-NMR. The chemical shift values were indicated by δ values (ppm), and the coupling constants were in Hertz. Also, s is the abbreviation for singlet, d for doublet, and m for multiplet. The content of the obtained NMR spectrum is as follows. δ = 12.05 (s, 3H), 8.70 (d, J = 8.4 Hz, 3H), 8.07 (d, J = 8.8 Hz, 3H), 7.93 (d, J = 8.0 Hz, 3H), 7.46 - 7.50 (m, 3H), 7.38 - 7.42 (m, 3H), 7.34 (d, J = 9.2 Hz, 3H)

[0094] As described above, in this specification, the ultraviolet-absorbing dye (A-1) was used as an example for structure identification by NMR. Other ultraviolet-absorbing dyes were also identified by NMR in the same manner as above, but the data are omitted.

[0095] [Ultraviolet-absorbing dye (A-2)] In the production of the ultraviolet-absorbing dye (A-1), the ultraviolet-absorbing dye (A-2) was obtained by a similar method except that 1,3-dihydroxynaphthalene was added instead of 2-naphthol.

[0096] [Ultraviolet-absorbing dye (A-3)] In the production of the ultraviolet-absorbing dye (A-1), the ultraviolet-absorbing dye (A-3) was obtained by a similar method except that 6-bromo-2-naphthol was added instead of 2-naphthol.

[0097] [Ultraviolet-absorbing dye (A-4)] In a 200 mL Erlenmeyer flask, 100 parts of N-methyl-2-pyrrolidone, 20.0 mmol of ultraviolet-absorbing dye (A-1), and 40.0 mmol of potassium carbonate were charged, and the mixture was heated to 90 °C with stirring. Next, 40.0 mmol of 1-iodohexane was charged, and the mixture was stirred at 90 °C for 4 hours. On the other hand, 500 parts of water was charged into a 1 L beaker, and the previous reaction solution was added dropwise little by little. The precipitate was filtered off and washed by sprinkling with 500 parts of water. The obtained wet cake was returned to 500 parts of water, slurried at room temperature for 30 minutes, and then filtered. Thereafter, it was washed by sprinkling with 500 parts of water. The obtained wet cake was dried at 80 °C overnight to obtain ultraviolet-absorbing dye (A-4).

[0098] [Ultraviolet-absorbing dye (A-5)] In a 200 mL Erlenmeyer flask, 100 parts of N-methyl-2-pyrrolidone, 20.0 mmol of ultraviolet-absorbing dye (A-2), and 60.0 mmol of potassium carbonate were charged, and the mixture was heated to 90 °C with stirring. Next, 60.0 mmol of 1-iodobutane was charged, and the mixture was stirred at 90 °C for 4 hours. On the other hand, 500 parts of water was charged into a 1 L beaker, and the previous reaction solution was added dropwise little by little. The precipitate was filtered off and washed by sprinkling with 500 parts of water. The obtained wet cake was returned to 500 parts of water, slurried at room temperature for 30 minutes, and then filtered. Thereafter, it was washed by sprinkling with 500 parts of water. The obtained wet cake was dried at 80 °C overnight to obtain ultraviolet-absorbing dye (A-5).

[0099] [Ultraviolet-absorbing dye (A-6)] In the production of ultraviolet-absorbing dye (A-1), ultraviolet-absorbing dye (A-6) was obtained in the same manner except that 6-hydroxy-2-naphthonitrile was added instead of 2-naphthol.

[0100] [Ultraviolet-absorbing dye (A-7)] In the production of ultraviolet-absorbing dye (A-1), ultraviolet-absorbing dye (A-7) was obtained in the same manner except that 6-hydroxy-2-naphthoic acid was added instead of 2-naphthol.

[0101] [Ultraviolet-absorbing dye (A-8)] In the production of the ultraviolet-absorbing dye (A-1), the ultraviolet-absorbing dye (A-8) was obtained in the same manner except that methyl 6-hydroxy-2-naphthoate was added instead of 2-naphthol.

[0102] [Ultraviolet-absorbing dye (A-9)] In the production of the ultraviolet-absorbing dye (A-1), the ultraviolet-absorbing dye (A-9) was obtained in the same manner except that sodium 2-naphthol-6-sulfonate hydrate was added instead of 2-naphthol.

[0103] [Ultraviolet-absorbing dye (A-10)] In the production of the ultraviolet-absorbing dye (A-1), the ultraviolet-absorbing dye (A-10) was obtained in the same manner except that 3-hydroxy-2-naphthoic acid was added instead of 2-naphthol.

[0104] [Ultraviolet-absorbing dye (A-11)] In the production of the ultraviolet-absorbing dye (A-1), the ultraviolet-absorbing dye (A-11) was obtained in the same manner except that methyl 3-hydroxy-2-naphthoate was added instead of 2-naphthol.

[0105] [2,4,6-Tris(2,7-dihydroxynaphthyl)-1,3,5-triazine] In the production of the ultraviolet-absorbing dye (A-1), 2,4,6-tris(2,7-dihydroxynaphthyl)-1,3,5-triazine was obtained in the same manner except that 2,7-dihydroxynaphthalene was added instead of 2-naphthol.

[0106] [Ultraviolet-absorbing dye (A-12)] Into a 200 mL Erlenmeyer flask, 100 parts of N-methyl-2-pyrrolidone, 20.0 mmol of 2,4,6-tris(2,7-dihydroxynaphthyl)-1,3,5-triazine, and 60.0 mmol of triethylamine were charged. While stirring, 60.0 mmol of acetyl chloride was charged, and the mixture was stirred at room temperature for 4 hours. On the other hand, 500 parts of water was charged into a 1 L beaker, and the previous reaction solution was added dropwise little by little. The precipitate was filtered off and washed by sprinkling with 500 parts of water. The obtained wet cake was returned to 500 parts of water and slurried at room temperature for 30 minutes, then filtered. Thereafter, washing by sprinkling with 500 parts of water was carried out. The obtained wet cake was dried at 80 °C overnight to obtain an ultraviolet-absorbing dye (A-12).

[0107] [Ultraviolet-absorbing dye (A-13)] In the production of the ultraviolet-absorbing dye (A-13), it was produced in the same manner except that pivaloyl chloride was added instead of acetyl chloride to obtain the ultraviolet-absorbing dye (A-13).

[0108] [Ultraviolet-absorbing dye (A-14)] In the production of the ultraviolet-absorbing dye (A-14), it was produced in the same manner except that 5-acetyl-2-naphthol was added instead of 2-naphthol to obtain the ultraviolet-absorbing dye (A-14).

[0109] [Ultraviolet-absorbing dye (A-15)] In the production of the ultraviolet-absorbing dye (A-15), it was produced in the same manner except that 3-hydroxy-2-naphthanilide was added instead of 2-naphthol to obtain the ultraviolet-absorbing dye (A-15).

[0110] [Ultraviolet-absorbing dye (A-16)] In the production of the ultraviolet-absorbing dye (A-16), it was produced in the same manner except that 3-hydroxy-2'-methoxy-2-naphthanilide was added instead of 2-naphthol to obtain the ultraviolet-absorbing dye (A-16).

[0111] [Ultraviolet-absorbing dye (A-17)] In the production of the ultraviolet-absorbing dye (A-1), the ultraviolet-absorbing dye (A-17) was obtained in the same manner except that 5'-chloro-3-hydroxy-2'-methyl-2-naphthanilide was added instead of 2-naphthol.

[0112] [Ultraviolet-absorbing dye (A-18)] In the production of the ultraviolet-absorbing dye (A-1), the ultraviolet-absorbing dye (A-18) was obtained in the same manner except that 5'-chloro-3-hydroxy-2'-methoxy-2-naphthanilide was added instead of 2-naphthol.

[0113] [Ultraviolet-absorbing dye (A-19)] In the production of the ultraviolet-absorbing dye (A-1), the ultraviolet-absorbing dye (A-19) was obtained in the same manner except that 3-hydroxy-3'-nitro-2-naphthanilide was added instead of 2-naphthol.

[0114] [Ultraviolet-absorbing dye (A-20)] Into a 200 mL Erlenmeyer flask, 100 parts of N-methyl-2-pyrrolidone, 20.0 mmol of the ultraviolet-absorbing dye (A-1), and 60.0 mmol of triethylamine were charged. While stirring, 40.0 mmol of acryloyl chloride was charged, and the mixture was stirred at room temperature for 4 hours. On the other hand, 500 parts of water was charged into a 1 L beaker, and the previous reaction solution was added dropwise little by little. The precipitate was filtered off and washed by sprinkling with 500 parts of water. The obtained wet cake was returned to 500 parts of water and slurried at room temperature for 30 minutes, and then filtered off. Thereafter, washing by sprinkling with 500 parts of water was performed. The obtained wet cake was dried at 80 °C overnight to obtain the ultraviolet-absorbing dye (A-20).

[0115] [Ultraviolet-absorbing dye (A-21)] Into a 200 mL Erlenmeyer flask, 100 parts of N-methyl-2-pyrrolidone and 20.0 mmol of 2-methacryloyloxyethyl succinic acid (Light Ester HO-MS(N), manufactured by Kyoeisha Chemical Co., Ltd.) were charged, and the mixture was stirred while cooling with ice. 20 mmol of thionyl chloride was added dropwise, and the mixture was stirred for 2 hours while cooling with ice. Then, 20.0 mmol of the ultraviolet-absorbing dye (A-1) was charged, and the mixture was stirred at room temperature for 4 hours. On the other hand, 500 parts of water was charged into a 1 L beaker, and the previous reaction solution was added dropwise little by little. The precipitate was filtered off and washed by sprinkling with 500 parts of water. The obtained wet cake was returned to 500 parts of water, reslurried at room temperature for 30 minutes, and then filtered off. Thereafter, it was washed by sprinkling with 500 parts of water. The obtained wet cake was dried at 80 °C overnight to obtain the ultraviolet-absorbing dye (A-21).

[0116] [Ultraviolet-absorbing dye (A-22)] Into a 200 mL Erlenmeyer flask, 100 parts of N-methyl-2-pyrrolidone and 40.0 mmol of 2-methacryloyloxyethyl succinic acid (Light Ester HO-MS(N), manufactured by Kyoeisha Chemical Co., Ltd.) were charged, and the mixture was stirred while cooling with ice. 40 mmol of thionyl chloride was added dropwise, and the mixture was stirred for 2 hours while cooling with ice. Then, 20.0 mmol of the ultraviolet-absorbing dye (A-1) was charged, and the mixture was stirred at room temperature for 4 hours. On the other hand, 500 parts of water was charged into a 1 L beaker, and the previous reaction solution was added dropwise little by little. The precipitate was filtered off and washed by sprinkling with 500 parts of water. The obtained wet cake was returned to 500 parts of water, reslurried at room temperature for 30 minutes, and then filtered off. Thereafter, it was washed by sprinkling with 500 parts of water. The obtained wet cake was dried at 80 °C overnight to obtain the ultraviolet-absorbing dye (A-22).

[0117] [Ultraviolet-absorbing dye (A-23)] In the production of the ultraviolet-absorbing dye (A-22), the ultraviolet-absorbing dye (A-23) was obtained in the same manner except that ω-carboxy polycaprolactone (n≈2) monoacrylate (Aronix M-5300, manufactured by Toagosei Co., Ltd.) was added instead of 2-methacryloyloxyethyl succinic acid (Light Ester HO-MS(N), manufactured by Kyoeisha Chemical Co., Ltd.).

[0118] [Ultraviolet-absorbing dye (A-24)] In the production of the ultraviolet-absorbing dye (A-22), the ultraviolet-absorbing dye (A-24) was obtained in the same manner except that phthalic acid mono-hydroxyethyl acrylate (Aronix M-5400, manufactured by Toagosei Co., Ltd.) was added instead of 2-methacryloyloxyethyl succinic acid (Light Ester HO-MS(N), manufactured by Kyoeisha Chemical Co., Ltd.).

[0119] [Ultraviolet-absorbing dye (A-25)] In a 300 mL Erlenmeyer flask, 170 parts of chlorobenzene, 43.4 mmol of 2-chloro-4,6-di(naphthalen-1-yl)-1,3,5-triazine, and 65.1 mmol of aluminum chloride were charged and stirred to form a suspension. Next, 65.1 mmol of 2-naphthol was added little by little while cooling with ice water. Then, the mixture was gradually returned to room temperature and stirred overnight. On the other hand, 38.1 parts of water, 10.0 parts of 35% hydrochloric acid, and 45.0 parts of methanol were charged into a 500 mL beaker, and the previous reaction solution was added dropwise little by little. Further, 45.0 parts of methanol was added to the Erlenmeyer flask in multiple portions while washing, and added to the 500 mL beaker. The precipitate was filtered off and washed by sprinkling with a mixed solvent of water / methanol = 75 parts / 75 parts. The obtained wet cake was returned to 150 parts of water and slurried at room temperature for 30 minutes, and then filtered off. Thereafter, it was washed by sprinkling with 150 parts of water. The obtained wet cake was dried at 80 °C overnight to obtain the ultraviolet-absorbing dye (A-25).

[0120] [Ultraviolet-absorbing dye (A-26)] 170 parts of chlorobenzene, 43.4 mmol of 2,4-dichloro-6-phenyl-1,3,5-triazine, and 65.1 mmol of aluminum chloride were charged into a 300 mL Erlenmeyer flask and stirred to form a suspension. Next, 108.5 mmol of 2-naphthol was added little by little while cooling with ice water. Then, the mixture was stirred overnight while gradually returning to room temperature. On the other hand, 38.1 parts of water, 10.0 parts of 35% hydrochloric acid, and 45.0 parts of methanol were charged into a 500 mL beaker, and the previous reaction solution was added dropwise little by little. Further, 45.0 parts of methanol was added to the Erlenmeyer flask in multiple portions while washing and added to the 500 mL beaker. The precipitate was filtered off and rinsed with a mixed solvent of water / methanol = 75 parts / 75 parts. The obtained wet cake was returned to 150 parts of water and slurried at room temperature for 30 minutes, then filtered off. Thereafter, it was rinsed with 150 parts of water. The obtained wet cake was dried at 80 °C overnight to obtain an ultraviolet-absorbing dye (A-26).

[0121] [Ultraviolet-absorbing dye (A-27)] In the production of the ultraviolet-absorbing dye (A-26), the ultraviolet-absorbing dye (A-27) was obtained in the same manner except that 2-(4-biphenylyl)-4,6-dichloro-1,3,5-triazine was added instead of 2,4-dichloro-6-phenyl-1,3,5-triazine.

[0122] [Production 1 of ultraviolet-absorbing dye (A-28)] In the production of the ultraviolet-absorbing dye (A-25), the ultraviolet-absorbing dye (A-28) was obtained in the same manner except that 2-chloro-4,6-diphenyl-1,3,5-triazine was added instead of 2-chloro-4,6-di(naphthalen-1-yl)-1,3,5-triazine.

[0123] [Production 2 of ultraviolet-absorbing dye (A-28)] 420 mmol of methyl 2-hydroxy-1-naphthoate was charged into a 500 mL Erlenmeyer flask and heated to 90 °C with stirring. Next, 128 mmol of benzamidine hydrochloride and 26 parts of a 30% solution of sodium methylate were charged, and the mixture was stirred at 90 °C for 22 hours. Thereafter, 200 parts of methanol was charged, the mixture was cooled to room temperature, and filtered. The obtained wet cake was returned to 150 parts of methanol and slurried at room temperature for 30 minutes, and then filtered. Thereafter, it was washed by sprinkling with 150 parts of methanol. The obtained wet cake was dried at 80 °C overnight to obtain an ultraviolet-absorbing dye (A-28). The ultraviolet-absorbing dye (A-28) produced in this way synthesized the same compound (A-28) by a synthetic route different from that of Production 1 above.

[0124] [Ultraviolet-absorbing dye (A-29)] In the production of the ultraviolet-absorbing dye (A-28-2), an ultraviolet-absorbing dye (A-29) was obtained in the same manner except that p-methylbenzamidine hydrochloride was added instead of benzamidine hydrochloride.

[0125] [Ultraviolet-absorbing dye (A-30)] In the production of the ultraviolet-absorbing dye (A-28-2), an ultraviolet-absorbing dye (A-30) was obtained in the same manner except that p-butoxybenzamidine hydrochloride was added instead of benzamidine hydrochloride.

[0126] [Ultraviolet-absorbing dye (A-31)] In the production of the ultraviolet-absorbing dye (A-25), an ultraviolet-absorbing dye (A-31) was obtained in the same manner except that 2-chloro-4,6-dimethoxy-1,3,5-triazine was added instead of 2-chloro-4,6-di(naphthalen-1-yl)-1,3,5-triazine.

[0127] [Ultraviolet-absorbing dye (A-32)] In the production of the ultraviolet-absorbing dye (A-25), 2,4-bis[4-(tert-butyl) Manufactured in the same manner except that phenyl]-6-chloro-1,3,5-triazine was added to obtain an ultraviolet-absorbing dye (A-32).

[0128] [Ultraviolet-absorbing dye (A-33)] In the production of the ultraviolet-absorbing dye (A-25), it was manufactured in the same manner except that 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine was added instead of 2-chloro-4,6-di(naphthalen-1-yl)-1,3,5-triazine, and the ultraviolet-absorbing dye (A-33) was obtained.

[0129] (Production Examples 1-1 to 1-35, Comparative Dyes 1 to 6) Table 1 shows the results of measuring the ultraviolet-visible absorption spectra of the ultraviolet-absorbing dyes (A-1) to (A-33) and the comparative dyes (AA-1) to (AA-3). The following ultraviolet-absorbing agents were used as the comparative dyes. For all of these ultraviolet-absorbing agents, the light transmittance was confirmed to be less than 10% in the wavelength range of 320 nm or more and less than 400 nm, and then the visible light absorbability and the like were evaluated.

[0130] (AA-1) Tinuvin 970 (manufactured by BASF Japan Ltd., benzotriazole-based ultraviolet absorber) (AA-2) Tinuvin 460 (manufactured by BASF Japan Ltd., triazine-based ultraviolet absorber) (AA-3) LA-F70 (manufactured by ADEKA Corporation, triazine-based ultraviolet absorber)

[0131] (AA-1) is a benzotriazole-based ultraviolet absorber and has a structure different from that of the present invention. (AA-2) and (AA-3) are triazine-based ultraviolet absorbers and do not have a naphthalene ring, respectively.

[0132] Also, the method for preparing the solution for absorbance measurement and the measurement conditions are as follows.

[0133] <Solution preparation method> 1 part of ultraviolet-absorbing dye (A-1) and 1000 parts of tetrahydrofuran were mixed and completely dissolved. Subsequently, 1 part of the above-mentioned solution and 99 parts of tetrahydrofuran were uniformly mixed to prepare a solution with a concentration of 10 ppm.

[0134] Regarding the ultraviolet absorbers of ultraviolet-absorbing dyes (A-2) to (A-33) and comparative dyes (AA-1) to (AA-3), they were also adjusted to the concentrations shown in Table 1.

[0135] <Measurement conditions> Apparatus: Ultraviolet-visible-near-infrared spectrophotometer U-3500 (manufactured by Hitachi, Ltd.) Measurement wavelength: 260 - 700 nm Solvent: Tetrahydrofuran Concentration: As described in Table 1

[0136] The evaluation criteria for ultraviolet-visible absorption spectra are as follows. ◎: Absorbance at wavelengths of 400 - 420 nm is 0.3 or more over the entire region: Good 〇: Absorbance at wavelengths of 400 - 420 nm is 0.3 or more in part and less than 0.3 in the others: Practical range △: Absorbance at wavelengths of 400 - 420 nm is 0.1 or more and less than 0.3 in part and less than 0.1 in the others: Not practical ×: Absorbance at wavelengths of 400 - 420 nm is less than 0.1 over the entire region: Not practical

[0137]

Table 1

[0138] As shown in Table 1, it can be seen that the ultraviolet-absorbing dye (A) used in the resin composition of the present invention has a higher absorbance per unit weight in the short-wavelength visible light region of 400 - 420 nm compared with the ultraviolet absorber (AA) used in the conventional resin composition.

[0139] <Thermoplastic resins (B)(C)> (B-1) Polyester MA-2101M (polyester resin, manufactured by Unitika Ltd., crystalline resin, melting point 264°C, MFR 45 g / 10 min (280°C / 2.16 kg)) (B-2) Iupilon S-3000 (polycarbonate resin, manufactured by Mitsubishi Engineering-Plastics Corporation, amorphous resin, glass transition temperature 145°C, MFR 15 g / 10 min (300°C / 1.2 kg)) (B-3) Topas 6013M-07 (cycloolefin resin, manufactured by Polyplastics Co., Ltd., amorphous resin, glass transition temperature 142°C, MFR 13 g / 10 min (260°C / 2.16 kg)) (B-4) Apel (cycloolefin resin, manufactured by Mitsui Chemicals, Inc., amorphous resin, glass transition temperature 135°C, MFR 11 g / 10 min or more (260°C / 2.16 kg)) (B-5) Amilan CM3001-N (polyamide resin, manufactured by Toray Industries, Inc., crystalline resin, melting point 265°C, MFR 7 g / 10 min or more (235°C / 2.16 kg)) (B-6) ULTEM (polyetherimide resin, manufactured by Saudi Basic Industries Corporation, amorphous resin, glass transition temperature 217°C, MFR 8 g / 10 min or more (337°C / 6.6 kg)) (C-1) Suntech LD M2270 (polyethylene resin, manufactured by Asahi Kasei Chemicals Corporation, crystalline resin, melting point 110°C, MFR 7 g / 10 min (180°C / 2.16 kg)) (C-2) Acrypet MF (polymethacrylic resin, manufactured by Mitsubishi Rayon Co., Ltd., amorphous resin, glass transition temperature 100°C, MFR 14 g / 10 min (230°C / 3.8 kg))

[0140] <Liquid Resin (E)> (E-1): Unionol D-1200 (manufactured by NOF Corporation, polyalkylene glycol resin, polypropylene glycol resin, number average molecular weight 1200, viscosity 200 mPa·s) (E-2): PEG-400 (manufactured by Sanyo Chemical Industries, Ltd., polyalkylene glycol resin, polypropylene glycol resin, number average molecular weight 400, viscosity 90 mPa·s) (E-3): Unionol D-400 (manufactured by NOF Corporation, polyalkylene glycol resin, polypropylene glycol resin, number average molecular weight 400, viscosity 100 mPa·s) (E-4): Adeka Sizer RS-107 (manufactured by ADEKA Corporation, ether ester resin, adipic acid ether ester resin, number average molecular weight 430, viscosity 20 mPa·s) (E-5): Adeka Sizer RS-700 (manufactured by ADEKA Corporation, ether ester resin, number average molecular weight 550, viscosity 30 mPa·s) (E-6): Adeka Sizer PN-250 (manufactured by ADEKA Corporation, fatty acid polyester resin, adipic acid polyester resin, number average molecular weight 2100, viscosity 4,500 mPa·s) (E-7): Adeka Sizer PN-350 (manufactured by ADEKA Corporation, fatty acid polyester resin, adipic acid polyester resin, number average molecular weight 4500, viscosity 10,000 mPa·s)

[0141] <Resin-type dispersant (G)> (Manufacture of resin-type dispersant solution (G-1)) To BYK-LPN6919 manufactured by BYK-Chemie Japan with a non-volatile content of 60%, an equal amount of liquid resin (E-4) was added, heated to 100 °C and the solvent was distilled off under reduced pressure to obtain a resin-type dispersant solution (G-1) with a non-volatile content of BYK-LPN6919 / liquid resin (E-4) = 1 / 1.

[0142] [Synthesis of ethylenically unsaturated monomer (b-5)] Into a reaction vessel equipped with a stirrer and a thermometer, 60 parts of 2-isocyanatoethyl methacrylate, 29 parts of 3-(dimethylamino)propylamine, and 120 parts of tetrahydrofuran (THF) were charged and stirred at room temperature for 5 hours. After confirming by FT-IR that the reaction was complete, the solvent was distilled off using a rotary evaporator to obtain 73 parts (yield 82%) of the following ethylenically unsaturated monomer (b-5) as a pale yellow transparent liquid. Identification of the obtained compound was carried out by 1H-NMR.

[0143] [Synthesis of ethylenically unsaturated monomer (b-9)] Into a reaction vessel equipped with a stirrer and a thermometer, 6.6 parts of ethylenically unsaturated monomer (b-5) obtained by the synthesis of ethylenically unsaturated monomer (b-5) and 5 parts of ion-exchanged water were charged, and after stirring at room temperature, 8 parts of a 35% hydrochloric acid aqueous solution were added dropwise. It was confirmed by amine value measurement that the reaction was complete, and 20 parts of an aqueous solution of ethylenically unsaturated monomer (b-9) was obtained as a pale yellow transparent liquid. The obtained compound was identified by 1H-NMR.

[0144] [Chemical formula]

[0145] (Production of resin-type dispersant solution (G-2)) Into a reaction tank equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 17.7 parts of methyl methacrylate, 53.2 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and the mixture was stirred at 50 °C for 1 hour while flowing nitrogen, and the system was purged with nitrogen. Next, 2.6 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 100 parts of PGMAc were charged, and the temperature was raised to 110 °C under a nitrogen stream to initiate the polymerization of the first block. After 4 hours of polymerization, the polymerization solution was sampled for non-volatile content measurement, and it was confirmed that the polymerization conversion rate was 98% or more in terms of non-volatile content. Next, 20 parts of PGMAc, 21.2 parts of ethylenically unsaturated monomer (b-5) as the second block monomer, and 27 parts of an aqueous solution of ethylenically unsaturated monomer (b-9) (non-volatile content 38%) were added to this reaction tank, and the mixture was stirred while maintaining the temperature at 110 °C in a nitrogen atmosphere to continue the reaction. After 2 hours, the polymerization solution was sampled for non-volatile content measurement, and it was confirmed that the polymerization conversion rate of the second block was 98% or more in terms of non-volatile content, and the reaction solution was cooled to room temperature to stop the polymerization. PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content became 40% by mass. In this way, a resin-type dispersant solution with an amine value of 50 mgKOH / g, a quaternary ammonium salt value of 20 mgKOH / g, a weight average molecular weight (Mw) of 9,800, and a non-volatile content of 40% by mass was obtained. Furthermore, an amount of liquid resin (E-4) equal to the non-volatile content of this resin-type dispersant solution was added, heated to 100 °C, and the pressure was reduced to distill off PGMAc and water, thereby obtaining a resin-type dispersant solution (G-2) with a non-volatile content of the resin-type dispersant solution / liquid resin (E-4) = 1 / 1.

[0146] (Example 1-1) <Manufacture of Masterbatch> 2 parts of ultraviolet-absorbing dye (A-1) and 98 parts of thermoplastic resin (B-1) were fed into a twin-screw extruder (manufactured by Nippon Steel Works, Ltd.) with a screw diameter of 30 mm from the same supply port, melt-kneaded at 300 °C, and then cut into pellets using a pelletizer to prepare a masterbatch (D-1).

[0147] <Film Forming> To 90 parts of the thermoplastic resin (B-1) of the diluting resin, 10 parts of the obtained masterbatch (D-1) was mixed, melt-mixed at a temperature of 300 °C using a T-die forming machine (manufactured by Toyo Seiki), and a film (X-1) with a thickness of 250 μm was formed.

[0148] (Examples 1-2 to 1-40, Comparative Examples 1-1 to 1-8) In the same manner as in Example 1-1, using the materials described in Tables 2-1 to 2-2, films (X-2) to (X-40), (Y-1) to (Y-8) with a thickness of 250 μm were formed.

[0149] (Example 1-41) <Manufacture of Liquid Masterbatch (F)> A liquid masterbatch (F-1) was prepared by kneading 10 parts of ultraviolet-absorbing dye (A-1) and 90 parts of liquid resin (E-1) with a roll.

[0150] <Film Forming> To 99.5 parts of the thermoplastic resin (B-3) of the diluting resin, 0.5 part of the obtained liquid masterbatch (F-1) was mixed, melt-mixed at a temperature of 300 °C using a T-die forming machine (manufactured by Toyo Seiki), and a film (X-41) with a thickness of 250 μm was formed.

[0151] (Examples 1-42 to 1-58) Similar to Example 1-41, films (X-42) to (X-58) with a thickness of 250 μm were formed using the materials described in Tables 2-1 to 2-2.

[0152] (Example 1-59) (Production of Liquid Masterbatch (F)) 10 parts of ultraviolet-absorbing dye (A-1), 20 parts of resin-type dispersant (G-1), and 70 parts of liquid resin (E-1) were dispersed with a bead mill to prepare liquid masterbatch (F-19).

[0153] (Film Forming) 0.5 part of the obtained liquid masterbatch (F-19) was mixed with 99.5 parts of thermoplastic resin (B-3) of the diluting resin, and melt-mixed at a temperature of 300 °C using a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.) to form a film (X-59) with a thickness of 250 μm.

[0154] (Examples 1-60 to 1-77) Similar to Example 1-59, films (X-60) to (X-77) with a thickness of 250 μm were formed using the materials described in Tables 2-1 to 2-2.

[0155] (Appearance Evaluation of Molded Products) Regarding (X-1) to (X-77) and (Y-1) to (Y-6), it was confirmed that uniform films were formed. For (Y-7) and (Y-8), it was confirmed that molded bodies with smooth surfaces could not be obtained and they were not suitable for applications with high molding processing temperatures such as engineering plastics.

[0156] (Ultraviolet Absorbency) The transmittance of the obtained film was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation), and it was evaluated whether the following conditions were satisfied. ◎: Light transmittance at wavelengths of 400 to 420 nm is less than 1% over the entire region: Good 〇: Light transmittance at wavelengths of 400 to 420 nm is less than 1% in part and 1% or more in others: Practical range △: Light transmittance at wavelengths of 400 - 420 nm is partially 1% or more and less than 10%, and the rest is 20% or more: Not practical ×: Light transmittance at wavelengths of 400 - 420 nm is 10% or more across the entire region: Not practical

[0157] [Transparency] The transparency of the obtained film was visually evaluated. The evaluation criteria are as follows. ○: No turbidity is observed. Good △: Slight turbidity is observed. Practical range ×: Obvious turbidity is observed. Not practical

[0158] [Light resistance] The obtained film was exposed for 100 hours in a xenon weather meter at an illuminance of 60 W / m² for wavelengths of 300 - 400 nm 2 . 〇: The reduction rate of the absorbance at the maximum absorption wavelength is less than 5% △: The reduction rate of the absorbance at the maximum absorption wavelength is 5% or more and less than 20% ×: The reduction rate of the absorbance at the maximum absorption wavelength is 20% or more

[0159] [Haze value] For the obtained film, the haze value was measured with a haze meter and evaluated according to the following criteria. ◎+: Less than 0.2 Extremely good ◎ : 0.2 or more and less than 0.5 Very good 〇 : 0.5 or more and less than 2 Good △ : 2 or more and less than 5 Good × : 5 or more Not practical

[0160]

Table 2-1

[0161]

Table 2-2

[0162] As shown in Tables 2-1 to 2-2, the resin molded article of the present invention has a low transmittance per unit weight in the short wavelength region of visible light of 400 to 420 nm. Since a small amount of an ultraviolet absorbing dye in the resin molded article reaches the practical range, the transparency of the film is good. In particular, compared with the resin molded article using Tinuvin 970 of the comparative example, it reaches the practical range with a small amount of addition, so it has excellent transparency.

[0163] (Example 2-1) <Manufacture of masterbatch> 2 parts of an ultraviolet absorbing dye (A-1) and 98 parts of a thermoplastic resin (B-1) were put into a twin-screw extruder (manufactured by Nippon Steel Works, Ltd.) with a screw diameter of 30 mm from the same supply port, melt-kneaded at 300 °C, and then cut into pellets using a pelletizer to produce a masterbatch (D-1).

[0164] <Film forming> To 90 parts of the thermoplastic resin (B-1) of the diluted resin, 10 parts of the obtained masterbatch (D-1) was mixed, and using a T-die molding machine (manufactured by Toyo Seiki), it was melt-mixed at a temperature of 300 °C to produce a resin composition. Then, after retaining at 300 °C for 20 minutes, a film (XX-1) with a thickness of 250 μm was formed.

[0165] (Examples 2-2 to 2-40, Comparative Examples 2-1 to 2-8) In the same manner as in Example 2-1, using the materials described in Table 2, films (XX-2) to (XX-40), (YY-1) to (YY-8) with a thickness of 250 μm were formed.

[0166] (Example 2-41) <Manufacture of liquid masterbatch (F)> A liquid masterbatch (F-1) was produced by kneading 10 parts of an ultraviolet absorbing dye (A-1) and 90 parts of a liquid resin (E-1) with a roll.

[0167] <Film forming> To 99.5 parts of the thermoplastic resin (B-3) of the diluting resin, 0.5 part of the obtained liquid masterbatch (F-1) was mixed, and using a T-die molding machine (manufactured by Toyo Seiki), melt mixing was carried out at a temperature of 300 °C to prepare a resin composition. Subsequently, after retaining at 300 °C for 20 minutes, a film (XX-41) with a thickness of 250 μm was molded.

[0168] (Examples 2-42 to 2-58) In the same manner as in Example 2-41, using the materials described in Table 2, films (XX-42) to (XX-58) with a thickness of 250 μm were molded.

[0169] (Example 2-59) (Manufacture of Liquid Masterbatch (F)) 10 parts of the ultraviolet-absorbing dye (A-1), 20 parts of the resin-type dispersant (G-1), and 70 parts of the liquid resin (E-1) were dispersed by a bead mill to prepare a liquid masterbatch (F-19).

[0170] (Film Molding) To 99.5 parts of the thermoplastic resin (B-3) of the diluting resin, 0.5 part of the obtained liquid masterbatch (F-19) was mixed, and using a T-die molding machine (manufactured by Toyo Seiki), melt mixing was carried out at a temperature of 300 °C to prepare a resin composition. Subsequently, after retaining at 300 °C for 20 minutes, a film (XX-59) with a thickness of 250 μm was molded.

[0171] (Examples 2-60 to 2-77) In the same manner as in Example 2-59, using the materials described in Table 2, films (XX-60) to (XX-77) with a thickness of 250 μm were molded.

[0172] [Appearance Evaluation of Molded Products] Regarding (XX-1) to (XX-77), (YY-1) to (YY-6), it was confirmed that a uniform film was formed. For (YY-7) and (YY-8), a molded body with a smooth surface could not be obtained, and it was confirmed that they were not suitable for applications with a high molding processing temperature such as engineering plastics.

[0173] [Ultraviolet Absorbency] The transmittance of the obtained film was measured using an ultraviolet-visible-near-infrared spectrophotometer (manufactured by Shimadzu Corporation), and it was evaluated whether the following conditions were satisfied or not. ◎: The light transmittance at wavelengths of 400 to 420 nm is less than 1% over the entire region: Good 〇: The light transmittance at wavelengths of 400 to 420 nm is less than 1% in part and 1% or more in the others: Practical range △: The light transmittance at wavelengths of 400 to 420 nm is 1% or more and less than 10% in part and 20% or more in the others: Not practical ×: The light transmittance at wavelengths of 400 to 420 nm is 10% or more over the entire region: Not practical

[0174] [Heat Resistance] Regarding the obtained films (XX-1) to (XX-77), (YY-1) to (YY-8), the differences in ultraviolet absorbency from the films (X-1) to (X-40), (Y-1) to (Y-8) obtained in Examples (1-1) to (1-77) and Comparative Examples (1-1) to (1-8) were compared and evaluated. The evaluation criteria are as follows. ◎: The difference in light transmittance at wavelengths of 400 to 420 nm is less than 1%: Good 〇: The difference in light transmittance at wavelengths of 400 to 420 nm is less than 5%: Practical range △: The difference in light transmittance at wavelengths of 400 to 420 nm is less than 10%: Not practical ×: The difference in light transmittance at wavelengths of 400 to 420 nm is 10% or more: Not practical

[0175] Note that since the raw materials and compounding ratios of Examples 2-1 to 2-77 and Comparative Examples 2-1 to 2-8 are the same as those of Examples 1-1 to 1-77 and Comparative Examples 1-1 to 1-8 respectively, only the results are described in Table 3.

[0176]

Table 3

[0177] As shown in Table 3, the resin molded product of the present invention has a small change rate of ultraviolet absorbency due to the residence time during melt mixing at the time of film molding. Therefore, it was confirmed that it has good heat resistance.

Claims

1. An ultraviolet-absorbing dye (A) that absorbs light in the ultraviolet region of less than 400 nm and the short-wavelength visible light region of 400 to 420 nm and is a compound selected from the group consisting of the following general formula (1), general formula (2), and general formula (3), and a melt-kneaded product of a thermoplastic resin (B), a resin composition for molding (excluding fiber applications), wherein the resin composition contains 0.001 to 5% by mass of the ultraviolet-absorbing dye (A), and the thermoplastic resin (B) is a crystalline resin having a melting point of 200 or higher or an amorphous resin having a glass transition temperature of 120 or higher, a resin composition for molding. 【Chemical 1】 (In general formulas (1) to (3), R ２ａ , R ３ａ is a hydroxyl group. R １ｂ to R １ｇ , R ２ｂ to R ２ｇ , R ３ｂ to R ３ｇ are each independently a hydrogen atom, a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitrile group, a nitro group, a sulfo group, R ７ , Ar １ , or a group represented by the following general formulas (4-1) to (4-3). R ７ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkenyloxy group having 1 to 20 carbon atoms, and may have a substituent of a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitrile group, a nitro group, a carboxyl group, or a sulfo group, and the carbon atoms of the alkyl group having 1 to 20 carbon atoms, the alkenyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms, or the alkenyloxy group having 1 to 20 carbon atoms may be linked by one or more of -O-, -CO-, -COO-, -OCO-, -CONH-, or -NHCO-. Ar １ is an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or a biphenyl group, and may have a substituent such as a hydroxyl group, an alkyl group having 1 to 20 carbon atoms (excluding an alkyl group having 1 carbon atom), an alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms (excluding a phenoxy group), a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitrile group, a nitro group, a carboxyl group, or a sulfo group. In general formulas (2) to (3), R ４ , R ５ , R ６ is a hydroxyl group, R ７ or Ar １ , and R ５ , R ６ are the same substituents. However, in general formula (3), R ５ or R ６ does not have a hydroxyphenyl group. However, the compounds of general formula (1), general formula (2), and general formula (3) exclude 1,1’,1’’-(1,3,5-triazine-2,4,6-triyl)tris[2-naphthalenol], 1,1’-(4-phenyl-1,3,5-triazine-2,6-diyl)bis[2-naphthalenol], 1-(4,6-diphenyl-1,3,5-triazine-2-yl)-2-naphthalenol General formula (4-1) 【Chemical Formula 2】 In the general formula (4-1), X １ is -CO-, -COO-, -OCO-, -CONH-, or -NHCO-. R ８ is a hydrogen atom, a hydroxyl group, R ７ or Ar １ However, * in the general formula (4-1) represents the bonding site with the naphthalene ring of the general formulas (1) to (3). General formula (4-2) [Chemical Formula 3] In the general formula (4-2), X 2 , X ３ are each independently -CO-, -COO-, -OCO- , -CONH-, or -NHCO-. R ９ is an arylene group having 6 to 20 carbon atoms. R １０ is R ７ or Ar １ Here, * in the general formula (4-2) represents the bonding site with the naphthalene ring of the general formulas (1) to (3). General formula (4-3) 【Chemical Formula 4】 In general formula (4-3), X ４ , X ５ are each independently -CO-, -COO-, -OCO-, -CONH-, or -NHCO-. R １１ is a linear or branched alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. R １２ is R ７ or Ar １ . n is 1 to 20. However, * in general formula (4-3) represents the bonding site with the naphthalene ring of general formulas (1) to (3).)

2. A molded article obtained by molding the resin composition for molding according to Claim 1.

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