Resin composition and molded article

Abstract

To provide a resin composition that can form a molding having heat resistance to withstand melting and kneading at 270°C or higher, absorbs not only ultraviolet rays of less than 400 nm but also light in the visible-light short-wavelength range of about 400-420 nm, and has excellent transparency.SOLUTION: A resin composition is a melted and kneaded product of a UV-absorbing dye (A) that absorbs ultraviolet rays of less than 400 nm and light in the visible-light short-wavelength range of 400-420 nm, which is a triazine compound bound to one, two or three naphthalene ring(s), and a thermoplastic resin (B). The thermoplastic resin (B) 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.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Conventionally, resin molded products (hereinafter referred to as molded products) have been used as packaging materials for pharmaceutical drugs, cosmetics, etc. It is known that the organic matter contained in these packaging materials generally deteriorates due to the action of ultraviolet rays contained in sunlight, etc.

[0003] It has been pointed out that not only ultraviolet rays of less than 400 nm but also light in the visible light short wavelength region of about 400 to 420 nm in sunlight can damage organic matter and the human body. Therefore, it is effective to suppress the deterioration of the contents by including an ultraviolet absorber that absorbs ultraviolet rays and light in the visible light short wavelength region of about 400 to 420 nm in a molded product. Furthermore, there is a demand for an ultraviolet absorber with excellent light resistance whose properties do not deteriorate due to exposure to ultraviolet rays over a long period of time.

[0004] Applications of the molded articles other than packaging materials include optical applications such as polarizing plate protective films used in liquid crystal displays, anti-reflection films, and surface films for preventing deterioration of light-emitting elements in organic EL displays.

[0005] These optical applications require high-temperature processing, but also require high dimensional stability. In particular, molded products using engineering plastics are processed at high temperatures, for example at 260 to 340°C, so UV absorbers must have heat resistance to withstand high temperatures.

[0006] Patent Documents 1 and 2 disclose benzotriazole-based ultraviolet absorbents that absorb light in the short wavelength region of visible light of about 400 to 420 nm. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2018-177696 A [Patent Document 2] Special Publication No. 2016-514756 Summary of the Invention [Problem to be solved by the invention]

[0008] However, conventional resin compositions have a problem that the heat resistance of the ultraviolet absorbent is low, and they cannot be used for moldings of thermoplastic resins with high melting points or high softening points (e.g., engineering plastics). In addition, in order to absorb visible light in the short wavelength region of about 400 to 420 nm, the absorption coefficient per unit weight is low, and the thickness of the molded body needs to be increased, so there is a problem that it cannot be made thin. On the other hand, there is also a problem that the transparency of the molded body decreases when the amount of the ultraviolet absorbent is increased.

[0009] The present invention aims to provide a resin composition that has heat resistance sufficient to withstand melt kneading at 270°C or higher, absorbs 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 can be used to mold a molded article having good transparency. [Means for solving the problem]

[0010] The resin composition of the present invention is a resin composition which is a melt-kneaded mixture of an ultraviolet absorbing dye (A), which is a triazine compound that absorbs light in the ultraviolet region of less than 400 nm and in the short wavelength visible region of 400 to 420 nm and is bonded to one, two or three naphthalene rings, and a thermoplastic resin (B), in which 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. Effect of the Invention

[0011] According to the present invention described above, it is possible to provide a resin composition that has heat resistance sufficient to withstand melt kneading at 270°C or higher, absorbs 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 can be used to mold a molded article having good transparency, and a molded article. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The resin composition of the present invention is a resin composition which is a melt-kneaded mixture of an ultraviolet absorbing dye (A), which is a triazine compound that absorbs light in the ultraviolet region of less than 400 nm and in the short wavelength visible region of 400 to 420 nm and is bonded to one, two or three naphthalene rings, and a thermoplastic resin (B), in which 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 visible light short wavelength region 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. In addition, the ultraviolet absorbing dye (A) of the present invention has an unexpected effect of enabling desired wavelength absorption with a smaller amount than conventionally added. In addition, since it is possible to absorb wavelengths with a small amount, the amount added can be reduced, and therefore it has an effect of improving transparency without reducing the transparency of the molded product. In addition, it is preferable that the naphthalene ring is directly bonded to the triazine ring without a linking group. In addition, 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 of the naphthalene ring.

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

[0015] (In general formulas (1) to (3), R 1b ~R 1g , R 2a ~R 2g , R 3a ~R 3gare 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, which may have a substituent such as 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 via 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, which may have a substituent such as 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 addition, in the general formulae (2) to (3), R4, R5, and R6 are a hydroxyl group, R7, or Ar1. General formula (4-1) [ka]

[0016] In the 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 the general formula (4-1) represents a bonding site with the naphthalene ring of the general formulae (1) to (3). General formula (4-2) [ka]

[0017] In the 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. 10 is R7 or Ar1, provided that * in general formula (4-2) represents the bonding site with the naphthalene ring of general formulae (1) to (3). General formula (4-3) [ka]

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

[0019] The group represented by formula (4-1) is preferably a group represented by formula (4). General formula (4) [ka]

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

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

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

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

[0024] The above triazine compound can be synthesized by using a known synthesis method for 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. In addition, a method of condensing methyl 2-hydroxy-1-naphthoate and benzamidine hydrochloride using sodium methoxide can be mentioned. The naphthalene ring connected to the triazine ring by a single bond and the substituents of R4, R5, and R6 can be introduced after the triazine structure is formed, or before the triazine structure is formed.

[0025] The content of the ultraviolet absorbing dye (A) is preferably from 0.001 to 5% by mass, and more preferably from 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. The melting point is preferably 500°C or lower. The glass transition temperature of the amorphous resin is preferably 130°C or higher. The glass transition temperature is preferably 300°C or lower. Both the melting point and the glass transition temperature can be measured by a differential scanning calorimeter, a thermogravimetric differential thermal analyzer, or the like.

[0027] Examples of crystalline resins having a melting point of 200° C. or higher include polyester resins, polyamide resins, polyacetal resins, polyphenylene sulfide resins, and polyether ether ketone resins. Examples of amorphous resins 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, and polycarbonate resins.

[0028] <Polyester resin> Polyester is a crystalline resin having an ester bond in the main chain of the molecule, and examples thereof include polycondensates synthesized from dicarboxylic acid (including its derivatives) and diol (dihydric alcohol or dihydric phenol); polycondensates synthesized from dicarboxylic acid (including its derivatives) and cyclic ether compounds; ring-opening polymers of cyclic ether compounds, etc. Polyesters include homopolymers of dicarboxylic acid and diol, copolymers using multiple raw materials, and polymer blends of these. The derivatives of dicarboxylic acid include acid anhydrides and esterified products. There are two types of dicarboxylic acid, aliphatic and aromatic, and aromatic dicarboxylic acids are more preferable because they improve heat resistance.

[0029] Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, m-phenylenedigolic acid, p-phenylenedigolic acid, diphenyldiacetic acid, diphenyl-p,p'-dicarboxylic acid, diphenyl-4,4'-diacetic acid, diphenylmethane-p,p'-dicarboxylic acid, diphenylethane-m,m'-dicarboxylic acid, stilbenzyl carboxylic 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, and the like. Examples of the carboxylic acid include 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, and 1,5-bis(2-methoxyphenoxy)-3-oxypentane-p,p'-dicarboxylic acid. Examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, adipic acid, suberic acid, magelaic acid, sebacic acid, dodecanedicarboxylic acid, undecanedicarboxylic acid, maleic acid, and fumaric acid.

[0030] Examples of dihydric alcohols include 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, etc. Among these, ethylene glycol, butane-1,4-diol, and cyclohexanedimethanol are preferred. Examples of dihydric phenols include hydroquinone, resorcinol, and bisphenol A. Examples of the cyclic ether compound include ethylene oxide and propylene oxide.

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

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

[0033] Examples of the carboxylic acid component include adipic acid, sebacic acid, isophthalic acid, terephthalic acid, etc. The carboxylic acid component may be a compound having three or more carboxyl groups. The compound (Am) having two or more amino groups may be, for example, a known compound, and examples thereof include aliphatic polyamines such as ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and triethylenetetramine; aliphatic polyamines including alicyclic polyamines such as isophoronediamine and dicyclohexylmethane-4,4'-diamine; aromatic polyamines such as phenylenediamine and xylylenediamine; and diamino alcohols such as 1,3-diamino-2-propanol, 1,4-diamino-2-butanol, 1-amino-3-(aminomethyl)-3,5,5-trimethylcyclohexane-1-ol, 4-(2-aminoethyl)-4,7,10-triazadecan-2-ol, and 3-(2-hydroxypropyl)-o-xylene-α,α'-diamine. Commercially available polyamide resins include, for example, nylon 6 (manufactured by Toray Industries, Inc.), nylon 66 (manufactured by Toray Industries, Inc.), nylon 610, 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 alicyclic structure include norbornene polymer, monocyclic olefin polymer, cyclic conjugated diene polymer, vinyl alicyclic hydrocarbon polymer, and hydrogenated products thereof. Among these, norbornene polymer is preferred because of its excellent moldability and transparency. Examples of norbornene monomer include 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]dodec-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> Polyetherimide resin is an amorphous resin with a glass transition temperature of over 180°C, and has good transparency, high strength, high heat resistance, high elastic modulus and wide range of chemical resistance, which is why it is widely used in a variety of applications such as automobiles, telecommunications, aerospace, electrical / electronics, transportation and healthcare. One process for the production of polyetherimide resins is by polymerization of an alkali metal salt of a dihydroxy aromatic compound, such as bisphenol A disodium salt (BPA·Na2), with a bis(halophthalimide). The molecular weight of the resulting polyetherimide resin can be controlled in two ways. The first method is to use a molar excess of the bis(halophthalimide) relative to the alkali metal salt of the dihydroxy aromatic compound. The second method is to prepare the bis(halophthalic anhydride) in the presence of a monofunctional compound, such as phthalic anhydride, which forms an end-capping agent. The phthalic anhydride reacts with a portion of the organic diamine to form a monohalo-bis(phthalimide). The monohalo-bis(phthalimide) serves as an end-capping agent in the polymerization step by reaction with the phenoxide end groups in the growing polymer chain. An example of a commercially available polyetherimide resin is ULTEM (manufactured by Saudi Basic Industries Corporation).

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

[0037] Examples of the aromatic dihydroxy compound include bis(hydroxyaryl)alkanes such as 2,2-bis(4-hydroxyphenyl)propane (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, and 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane; bis(hydroxyaryl)cycloalkanes such as 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, etc. Also, piperazine, dipiperidyl hydroquinone, resorcin, and 4,4'-dihydroxydiphenyls may be used in combination.

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

[0039] The viscosity average molecular weight of the polycarbonate resin is preferably 15,000 to 30,000, and more preferably 16,000 to 27,000. Note that 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), and Iupilon E-2000 (manufactured by Mitsubishi Engineering Plastics Corporation, viscosity average molecular weight 27,000).

[0041] Thermoplastic resin (B) can achieve both high fluidity and moldability if it has an appropriate melt flow rate (MFR). The MFR of each resin can be measured in accordance with 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 type of resin, 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 above the melting point or glass transition temperature (about 200 to 320° C.). The preferred MFR for each resin is explained below.

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

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

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

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

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

[0048] The resin composition of the present invention may contain additives other than the ultraviolet absorbing dye (A) and the thermoplastic resin (B). Examples of additives include near infrared absorbing agents, light stabilizers, antioxidants, colorants, waxes, etc. These additives may be compounds known in the art for use in molded articles.

[0049] The near infrared absorbing agent is used to impart near infrared absorbing ability to the molded article. Examples of the near infrared absorbing agent include cyanine-based, diimonium-based, squarylium-based, and saphthalocyanine-based compounds. The content of the near infrared absorbing agent 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 product. 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 or artificial light sources and becomes hot. The antioxidant is preferably, for example, a monophenol-based, bisphenol-based, polymeric phenol-based, sulfur-based, or phosphoric acid-based antioxidant. 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 disperse the ultraviolet absorbing dye more uniformly in the molded product. The dispersant is preferably, for example, polyolefin wax, fatty acid wax, fatty acid ester wax, partially saponified fatty acid ester wax, saponified fatty acid wax, etc. The content of the wax is preferably 50 to 250 parts by mass relative to 100 parts by mass of the ultraviolet absorbing dye (A).

[0053] <Preparation of Resin Composition> The method for producing a resin composition according to the present specification comprises melt-kneading an ultraviolet absorbing dye (A) which is a compound selected from the group consisting of general formulas (1), (2), and (3), and a thermoplastic resin (B), wherein 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 resin composition after melt-kneading is preferably cooled.

[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 high-temperature processing process is preferable. The upper limit of the melt-kneading temperature is not limited because it varies depending on the type of thermoplastic resin (B). If forced to give an upper limit, it is preferably 500°C or lower, more preferably 450°C or lower. In addition, the upper limit must be lower than the sublimation temperature or decomposition temperature of the ultraviolet absorbing dye (A).

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

[0056] The resin composition is preferably prepared as a so-called master batch. When a master batch is prepared and then melt-kneaded with a diluent resin (thermoplastic resin (B)) to prepare a molded body, the ultraviolet absorbing dye (A) can be easily dispersed uniformly in the molded body and aggregation of the ultraviolet absorbing dye (A) can be suppressed, compared with a molded body prepared without using the master batch. This improves the transparency of the molded body. The master batch is preferably molded into pellets using a pelletizer after the melt-kneading. When prepared as a master batch, the content of the ultraviolet absorbing dye (A) is preferably from 0.01 to 20% by mass, and more preferably from 0.05 to 2% by mass, in 100% by mass of the resin composition.

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

[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 of 10,000 mPa·s or less at 25°C. The viscosity is more preferably 10 to 5,000 mPa·s, and more preferably 100 to 3,000 mPa·s. If it is within the above range, the ultraviolet absorbing dye (A) can be easily dispersed in the liquid master batch. 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 master batch (F). By being within this range, for example, the melt viscosity during melt kneading 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 200 to 2000, more preferably 500 to 1500, and particularly preferably 1000 to 1500. With an Mn of 200 or more, it is easy to achieve both moldability and transparency. Furthermore, with an Mn of 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, and polyether ester resins. Even when the thermoplastic resin (B) is polyethylene terephthalate (PET), polycarbonate, or other resins that require high molding temperatures, fatty acid polyester resins, polyalkylene glycol resins, and polyether ester resins are preferred because they have high heat resistance and excellent antistatic properties.

[0062] [Fatty acid polyester resin] It is a resin obtained by reacting an aliphatic polycarboxylic acid with 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 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 polyhydric alcohols 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, and 1,12-octadecanediol; and polyalkylene glycols such as diethylene glycol and dipropylene glycol.

[0064] The aliphatic polyvalent carboxylic acids and polyhydric alcohols can each be used alone or in combination of two or more kinds.

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

[0066] Commercially available fatty acid polyester resins include, for example, Adeka Cizer PN-170 (manufactured by ADEKA Corporation, viscosity at 25°C 800 mPa·s, freezing point -15°C, adipic acid polyester resin), Adeka Cizer P-200 (manufactured by ADEKA Corporation, viscosity at 25°C 2,600 mPa·s, freezing point -20°C, adipic acid polyester resin), and Adeka Cizer PN-250 (manufactured by ADEKA Corporation, viscosity at 25°C 4,500 mPa·s, freezing point -20°C, adipic acid polyester resin).

[0067] [Polyether resin] The polyether resin is a resin having a repeating unit of an alkyleneoxy group. The alkyleneoxy group preferably has 1 to 6 carbon atoms. The polyether resin preferably has a viscosity of 10,000 mPa·s or less at 25°C. This viscosity is suitable for use in liquid masterbatches. The alkyleneoxy group preferably has 2 to 4 carbon atoms. This improves compatibility while suppressing water absorption.

[0068] Examples of polyether resins include polyethylene glycol, both of which have 2 carbon atoms in their repeating units, polytrimethylene glycol and polypropylene glycol, both of which have 3 carbon atoms in their repeating units, and polytetramethylene glycol and polybutylene glycol, both of which have 4 carbon atoms in their repeating units.

[0069] [Polyetherester resin] The polyether ester resin is an ester compound of an aliphatic polycarboxylic acid resin and an alkylene glycol resin. Commercially available polyether ester resins include, for example, Adeka Cizer RS-107 (manufactured by ADEKA Corporation, viscosity at 25°C 20 mPa s, freezing point -47°C, adipic acid ether ester resin) and Adeka Cizer RS-700 (manufactured by ADEKA Corporation, viscosity at 25°C 30 mPa s, freezing point -53°C, polyether ester resin).

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

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

[0072] Since the liquid master batch (F) contains the liquid resin (E) and is liquid, it has high fluidity when melt-kneaded with the thermoplastic resin (B), and can disperse the ultraviolet absorbing dye (A) very uniformly. In particular, the resin of engineering plastics, which has high heat resistance, has limited fluidity even at the melt-kneading temperature. Therefore, it is difficult to disperse uniformly due to the aggregation of the dye, and it is difficult to improve transparency. Therefore, in the case of the thermoplastic resin (B), which is a crystalline resin with a melting point of 200°C or more, or an amorphous resin with a glass transition temperature of 120°C or more, the liquid master batch (F) is effective in improving transparency. It is particularly effective in applications where high transparency is required, such as optical filters.

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

[0074] (Resin-type dispersant (G)) The liquid masterbatch (F) preferably contains a resin-type dispersant (G). This allows the ultraviolet absorbing dye (A) to be more uniformly dispersed in the liquid masterbatch, and the resulting molded product has even higher transparency. In addition, the inclusion of the resin-type dispersant (G) improves the storage stability of the liquid masterbatch.

[0075] The resin-type dispersant (G) is a compound having an adsorption site that has the property of being adsorbed to an ultraviolet absorbing dye, and a relaxation site that is compatible with components other than the ultraviolet absorbing dye. Examples of the resin-type dispersant (G) include polycarboxylates such as polyurethanes and polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylates, and modified products thereof, amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups, and salts thereof, and other oil-based dispersants, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphates.

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

[0077] Among the resin-type dispersants, polymer dispersants having a basic functional group are preferred because the viscosity of the dispersion is reduced with a small amount of addition.Furthermore, nitrogen-containing graft copolymers, nitrogen-containing acrylic block copolymers having functional groups including tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc. in the side chains, and urethane-based polymer dispersants are preferred.

[0078] The amount of the resin-type dispersant (G) used is preferably about 5 to 200% by mass relative to the ultraviolet absorbing dye (A), and from the viewpoint of film-forming properties, more preferably about 10 to 100% by mass.

[0079] Commercially available resin-type dispersants include, for example, DisperbYk-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, and 2155 manufactured by BYK Japan Co., Ltd. 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 manufactured by Lubrizol Japan , 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. manufactured by Chiba Japan Co., Ltd. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 440 2, 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., and Ajisper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0080] When the resin-type dispersant (G) is in a state of being dissolved in an organic solvent, it is preferable to add the liquid resin (E), and then heat under reduced pressure to distill off the solvent before use.

[0081] <Production method of liquid masterbatch (F)> The liquid master batch (F) can be prepared by mixing and dispersing the ultraviolet absorbing dye (A) and the liquid resin (E). The dispersion can be carried out in combination with a resin-type dispersant (G). The dispersion can be carried out using a dispersing device such as 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 an attritor.

[0082] The molded article of the present specification is preferably produced by molding a resin composition. The molded article can be produced by molding the resin composition as it is. When the resin composition is prepared as a master batch, the molded article can be produced by melt-kneading it together with a diluted resin (thermoplastic resin (B)) and then molding it. The mass ratio of the master batch (X) to the diluted resin (Y) is preferably X / Y=1 / 5 to 1 / 500. When the mass ratio is within this range, the molded article is likely to have good optical properties.

[0083] When a liquid masterbatch (F) is used as the masterbatch, it is more preferable that the liquid masterbatch (F) is contained in an amount of 0.1 to 5 mass% in 100 mass% of the resin composition.

[0084] <Application> The composition of the present invention can be used, for example, in food packaging materials, pharmaceutical packaging materials, displays, glass interlayers, and lenses.

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

[0086] The molded article used for display, glass interlayer, and lens applications may be any molded article made of a thermoplastic resin, but is preferably a film made of a resin having a transparent property 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), and cellulose ester resin.

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

[0088] In glass interlayer applications, the composition is used, for example, in laminated glass for automobiles, buildings, etc. Laminated glass using a molded article containing the above composition can absorb ultraviolet light and light in the short wavelength region of visible light contained in sunlight, thereby suppressing adverse effects on the eyes and human body.

[0089] In lens applications, the composition is used, for example, in lenses for eyeglasses, optical sensors, etc. In eyeglass applications, lenses using a molded article containing the composition can, for example, absorb ultraviolet light contained in sunlight and light in the short wavelength region of visible light, thereby suppressing adverse effects on the eyes and human body, and in optical sensor applications, can increase the sensitivity of the sensor by cutting off light of unnecessary wavelengths that can become noise.

[0090] The molded article of the present specification can be widely used in applications such as medical drugs, cosmetics, food containers and packaging materials, miscellaneous goods, textile products, pharmaceutical containers, various industrial coating materials, automobile parts, home appliances, building materials for houses, toiletries, etc. Furthermore, it can be widely used in applications such as display materials, sensor materials, optical control materials, etc. EXAMPLES

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

[0092] <Method for producing ultraviolet absorbing dye (A)> [Ultraviolet absorbing dye (A-1)] In a 300mL Erlenmeyer flask, 170 parts of chlorobenzene, 43.4 mmol of cyanuric chloride, and 65.1 mmol of aluminum chloride were charged and suspended by stirring. Next, while cooling with ice water, 151.8 mmol of 2-naphthol was added little by little. After that, the mixture was gradually returned to room temperature and stirred overnight. Meanwhile, 38.1 parts of water, 10.0 parts of 35% hydrochloric acid, and 45.0 parts of methanol were charged into a 500mL beaker, and the reaction solution was gradually added dropwise. Furthermore, 45.0 parts of methanol were added to the Erlenmeyer flask in several portions and added to the 500mL beaker while washing. The precipitate was filtered 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, reslurried at room temperature for 30 minutes, and filtered. Then, it was washed by sprinkling with 150 parts of water. The obtained wet cake was dried overnight at 80° C. to obtain an ultraviolet absorbing dye (A-1).

[0093] The NMR measurement of the ultraviolet absorbing dye (A-1) gave results supporting the above structure. The measurement conditions were as follows: <Measurement conditions> Equipment:BRUKER AVANCE400 Resonance frequency: 400MHz (1H-NMR) Solvent: Dimethylsulfoxide-d8 Tetramethylsilane was used as the internal standard for 1H-NMR, and the chemical shift values ​​were expressed in δ values ​​(ppm), and the coupling constants in Hertz. s stands for singlet, d for doublet, and m for multiplet. The contents of the obtained NMR spectrum are as follows. δ=12.05(s,3H),8.70(d,J=8.4Hz,3H),8.07(d,J=8.8Hz,3H),7.93(d,J=8.0Hz,3H),7.46-7.50(m,3H),7.38-7.42(m,3H),7.34(d,J=9.2Hz,3H)

[0094] As described above, in this specification, the structure of the ultraviolet absorbing dye (A-1) was identified by NMR as an example. The structures of the 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)] An ultraviolet absorbing dye (A-2) was obtained in the same manner as in the production of the ultraviolet absorbing dye (A-1), except that 1,3-dihydroxynaphthalene was used instead of 2-naphthol.

[0096] [Ultraviolet absorbing dye (A-3)] An ultraviolet absorbing dye (A-3) was obtained in the same manner as in the production of the ultraviolet absorbing dye (A-1), except that 6-bromo-2-naphthol was used 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. while stirring. Next, 40.0 mmol of 1-iodohexane was charged, and the mixture was stirred at 90 ° C. for 4 hours. Meanwhile, 500 parts of water were charged in a 1 L beaker, and the reaction solution was dripped little by little. The precipitate was filtered, 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 filtered. Then, 500 parts of water was sprinkled and washed. The obtained wet cake was dried overnight at 80 ° C. 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. while stirring. Next, 60.0 mmol of 1-iodobutane was charged, and the mixture was stirred at 90 ° C. for 4 hours. Meanwhile, 500 parts of water were charged in a 1 L beaker, and the reaction solution was dripped little by little. The precipitate was filtered, 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 filtered. Then, 500 parts of water was sprinkled and washed. The obtained wet cake was dried overnight at 80 ° C. to obtain ultraviolet absorbing dye (A-5).

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

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

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

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

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

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

[0105] [2,4,6-tris(2,7-dihydroxynaphthyl)-1,3,5-triazine] The same production method as in the production of the ultraviolet absorbing dye (A-1) was used except that 2,7-dihydroxynaphthalene was used instead of 2-naphthol, to obtain 2,4,6-tris(2,7-dihydroxynaphthyl)-1,3,5-triazine.

[0106] [Ultraviolet absorbing dye (A-12)] In 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, and 60.0 mmol of acetyl chloride was charged while stirring, and stirred at room temperature for 4 hours. Meanwhile, 500 parts of water were charged in a 1 L beaker, and the reaction solution was dripped little by little. The precipitate was filtered 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 filtered. Then, 500 parts of water were sprinkled and washed. The obtained wet cake was dried overnight at 80 ° C. to obtain an ultraviolet absorbing dye (A-12).

[0107] [Ultraviolet absorbing dye (A-13)] An ultraviolet absorbing dye (A-13) was obtained in the same manner as in the production of the ultraviolet absorbing dye (A-12), except that pivaloyl chloride was added instead of acetyl chloride.

[0108] [Ultraviolet absorbing dye (A-14)] An ultraviolet absorbing dye (A-14) was obtained in the same manner as in the production of the ultraviolet absorbing dye (A-1), except that 5-acetyl-2-naphthol was used instead of 2-naphthol.

[0109] [Ultraviolet absorbing dye (A-15)] An ultraviolet absorbing dye (A-15) was obtained in the same manner as in the production of the ultraviolet absorbing dye (A-1), except that 3-hydroxy-2-naphthanilide was used instead of 2-naphthol.

[0110] [Ultraviolet absorbing dye (A-16)] An ultraviolet absorbing dye (A-16) was obtained in the same manner as in the production of the ultraviolet absorbing dye (A-1), except that 3-hydroxy-2'-methoxy-2-naphthanilide was used instead of 2-naphthol.

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

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

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

[0114] [Ultraviolet absorbing dye (A-20)] In a 200 mL Erlenmeyer flask, 100 parts of N-methyl-2-pyrrolidone, 20.0 mmol of ultraviolet absorbing dye (A-1), and 60.0 mmol of triethylamine were charged, and 40.0 mmol of acryloyl chloride was charged while stirring, and stirred at room temperature for 4 hours. Meanwhile, 500 parts of water were charged in a 1 L beaker, and the reaction solution was dripped little by little. The precipitate was filtered 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 filtered. Then, 500 parts of water were sprinkled and washed. The obtained wet cake was dried overnight at 80 ° C. to obtain ultraviolet absorbing dye (A-20).

[0115] [Ultraviolet absorbing dye (A-21)] In 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) were charged and stirred while cooling with ice. 20 mmol of thionyl chloride was dropped and stirred for 2 hours while cooling with ice. Then, 20.0 mmol of ultraviolet absorbing dye (A-1) was charged and stirred at room temperature for 4 hours. Meanwhile, 500 parts of water was charged in a 1 L beaker and the previous reaction solution was dropped little by little. The precipitate was filtered and washed by sprinkling with 500 parts of water. The obtained wet cake was returned to 500 parts of water and reslurried at room temperature for 30 minutes, and filtered. Then, 500 parts of water was sprinkled and washed. The obtained wet cake was dried overnight at 80 ° C. to obtain ultraviolet absorbing dye (A-21).

[0116] [Ultraviolet absorbing dye (A-22)] In 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) were charged and stirred while cooling with ice. 40 mmol of thionyl chloride was dropped and stirred for 2 hours while cooling with ice. Then, 20.0 mmol of ultraviolet absorbing dye (A-1) was charged and stirred at room temperature for 4 hours. Meanwhile, 500 parts of water was charged in a 1 L beaker and the previous reaction solution was dropped little by little. The precipitate was filtered and washed by sprinkling with 500 parts of water. The obtained wet cake was returned to 500 parts of water and reslurried at room temperature for 30 minutes, and filtered. Then, 500 parts of water was sprinkled and washed. The obtained wet cake was dried overnight at 80 ° C. to obtain ultraviolet absorbing dye (A-22).

[0117] [Ultraviolet absorbing dye (A-23)] The ultraviolet absorbing dye (A-23) was obtained in the same manner as in the production of the ultraviolet absorbing dye (A-22), except that ω-carboxy-polycaprolactone (n≒2) monoacrylate (Aronix M-5300, manufactured by Toa Gosei 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)] An ultraviolet absorbing dye (A-24) was obtained in the same manner as in the production of the ultraviolet absorbing dye (A-22), except that monohydroxyethyl phthalate acrylate (Aronix M-5400, manufactured by Toa Gosei 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 300mL Erlenmeyer flask, 170 parts of chlorobenzene, 43.4 mmol of 2-chloro-4,6-di(naphthalene-1-yl)-1,3,5-triazine, and 65.1 mmol of aluminum chloride were charged and suspended by stirring. Next, while cooling with ice water, 65.1 mmol of 2-naphthol was added little by little. After that, the mixture was gradually returned to room temperature and stirred overnight. Meanwhile, 38.1 parts of water, 10.0 parts of 35% hydrochloric acid, and 45.0 parts of methanol were charged in a 500mL beaker, and the reaction solution was gradually added dropwise. Furthermore, 45.0 parts of methanol were added to the Erlenmeyer flask in several portions and added to the 500mL beaker while washing. The precipitate was filtered 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, reslurried at room temperature for 30 minutes, and filtered. Thereafter, 150 parts of water was sprinkled on the cake for washing, and the resulting wet cake was dried overnight at 80° C. to obtain an ultraviolet absorbing dye (A-25).

[0120] [Ultraviolet absorbing dye (A-26)] In a 300mL Erlenmeyer flask, 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 and suspended by stirring. Next, 108.5 mmol of 2-naphthol was gradually added while cooling with ice water. After that, the mixture was gradually returned to room temperature and stirred overnight. Meanwhile, 38.1 parts of water, 10.0 parts of 35% hydrochloric acid, and 45.0 parts of methanol were charged in a 500mL beaker, and the reaction solution was gradually added dropwise. Furthermore, 45.0 parts of methanol were added to the Erlenmeyer flask in several portions and added to the 500mL beaker while washing. The precipitate was filtered 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, reslurried at room temperature for 30 minutes, and filtered. Then, 150 parts of water was sprinkled and washed. The obtained wet cake was dried overnight at 80° C. to obtain an ultraviolet absorbing dye (A-26).

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

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

[0123] [Production of ultraviolet absorbing dye (A-28) 2] 420mmol of 2-hydroxy-1-naphthoic acid methyl ester was charged into a 500mL Erlenmeyer flask and heated to 90°C while stirring. Next, 128mmol of benzamidine hydrochloride and 26 parts of a 30% solution of sodium methylate were charged and stirred at 90°C for 22 hours. After this, 200 parts of methanol were charged, cooled to room temperature, and filtered. The obtained wet cake was returned to 150 parts of methanol, reslurried at room temperature for 30 minutes, and filtered. Then, 150 parts of methanol were sprinkled and washed. The obtained wet cake was dried overnight at 80°C to obtain ultraviolet absorbing dye (A-28). In this way, the ultraviolet absorbing dye (A-28) of Production 2 was synthesized from the same compound (A-28) by a synthetic route different from that of Production 1.

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

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

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

[0127] [Ultraviolet absorbing dye (A-32)] An ultraviolet absorbing dye (A-32) was obtained in the same manner as in the production of the ultraviolet absorbing dye (A-25), except that 2,4-bis[4-(tert-butyl)phenyl]-6-chloro-1,3,5-triazine was added instead of 2-chloro-4,6-di(naphthalene-1-yl)-1,3,5-triazine.

[0128] [Ultraviolet absorbing dye (A-33)] An ultraviolet absorbing dye (A-33) was obtained in the same manner as in the production of the ultraviolet absorbing dye (A-25), 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.

[0129] (Production Examples 1-1 to 1-35, Comparative Dyes 1 to 6) The results of measuring the ultraviolet to visible absorption spectrum of the ultraviolet absorbing dyes (A-1) to (A-33) and the comparative dyes (AA-1) to (AA-3) are shown in Table 1. The comparative dyes used were the ultraviolet absorbents listed below. All of these ultraviolet absorbents were confirmed to have a transmittance of less than 10% in the wavelength range of 320 nm or more and less than 400 nm, and then their visible light absorbance and other properties were evaluated.

[0130] (AA-1) Tinuvin 970 (BASF Japan, benzotriazole-based UV absorber) (AA-2) Tinuvin 460 (BASF Japan, triazine-based UV absorber) (AA-3) LA-F70 (ADEKA, triazine-based UV 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 neither of them has a naphthalene ring.

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

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

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

[0135] <Measurement conditions> Equipment: UV-visible near-infrared spectrophotometer U-3500 (manufactured by Hitachi, Ltd.) Measurement wavelength: 260~ 700nm Solvent: Tetrahydrofuran Concentration: See Table 1

[0136] The evaluation criteria for the ultraviolet to visible absorption spectrum are as follows: ◎: The absorbance is 0.3 or more over the entire wavelength range of 400 to 420 nm: Good ○: Some absorbance values ​​at wavelengths of 400 to 420 nm are 0.3 or more, while others are less than 0.3: Practical range △: Some absorbance values ​​at wavelengths of 400 to 420 nm are 0.1 or more but less than 0.3, others are less than 0.1: Not practical ×: The absorbance of the light at wavelengths of 400 to 420 nm is less than 0.1 over the entire range: not practical.

[0137] [Table 1]

[0138] As shown in Table 1, 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 to 420 nm compared to the ultraviolet absorber (AA) used in conventional resin compositions.

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

[0140] <Liquid Resin (E)> (E-1): Uniol D-1200 (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): Uniol D-400 (NOF Corporation, polyalkylene glycol resin, polypropylene glycol resin, number average molecular weight 400, viscosity 100 mPa s) (E-4): Adeka Cizer RS-107 (ADEKA Corporation, ether ester resin, adipic acid ether ester resin, number average molecular weight 430, viscosity 20 mPa s) (E-5): Adeka Cizer RS-700 (ADEKA Corporation, ether ester resin, number average molecular weight 550, viscosity 30 mPa s) (E-6): Adeka Cizer PN-250 (ADEKA Corporation, fatty acid polyester resin, adipic acid polyester resin, number average molecular weight 2100, viscosity 4,500 mPa s) (E-7): Adeka Cizer PN-350 (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)> (Production of Resin-Type Dispersant Solution (G-1)) BYK-LPN6919 manufactured by BYK Japan, which has a non-volatile content of 60%, was mixed with the same amount of liquid resin (E-4) as BYK-LPN6919, heated to 100°C, reduced pressure, and the solvent was distilled off 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)] In 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 that the reaction was complete by FT-IR, the solvent was distilled off with a rotary evaporator to obtain 73 parts of the following ethylenically unsaturated monomer (b-5) as a pale yellow transparent liquid (yield 82%). The obtained compound was identified by 1H-NMR.

[0143] [Synthesis of ethylenically unsaturated monomer (b-9)] In a reaction vessel equipped with a stirrer and a thermometer, 6.6 parts of the ethylenically unsaturated monomer (b-5) obtained by the synthesis of the 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% aqueous hydrochloric acid solution were added dropwise. The completion of the reaction was confirmed by amine value measurement, and 20 parts of an aqueous solution of the ethylenically unsaturated monomer (b-9) was obtained as a pale yellow transparent liquid. The obtained compound was identified by 1H-NMR.

[0144] [ka]

[0145] (Production of resin-type dispersant solution (G-2)) In a reaction vessel equipped with a gas inlet tube, a condenser, an agitator, 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 inside of the system was replaced 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 polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile 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 the reaction tank, and the reaction was continued by stirring while maintaining the temperature at 110°C under a nitrogen atmosphere. After 2 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate of the second block was 98% or more based on the non-volatile content. The reaction solution was then cooled to room temperature to terminate the polymerization. PGMAc was added to the block copolymer solution synthesized above so that the non-volatile content was 40% by mass. In this way, a resin-type dispersant solution was obtained with an amine value per non-volatile content 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. Furthermore, a liquid resin (E-4) in an amount equal to the non-volatile content of this resin-type dispersant solution was added, and the mixture was heated to 100°C and reduced pressure to distill off the PGMAc and water, thereby obtaining a resin-type dispersant solution (G-2) in which the non-volatile content of this resin-type dispersant solution / liquid resin (E-4)=1 / 1.

[0146] (Example 1-1) <Masterbatch manufacturing> Two parts of the ultraviolet absorbing dye (A-1) and 98 parts of the thermoplastic resin (B-1) were fed into a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) having a screw diameter of 30 mm through the same supply port, melt-kneaded at 300°C, and then cut into pellets using a pelletizer to produce a master batch (D-1).

[0147] <Film molding> 90 parts of the dilution resin thermoplastic resin (B-1) was mixed with 10 parts of the obtained master batch (D-1), and the mixture was 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-1) having a thickness of 250 μm.

[0148] (Examples 1-2 to 1-40, Comparative Examples 1-1 to 1-8) Similarly to Example 1-1, films (X-2) to (X-40) and (Y-1) to (Y-8) each having a thickness of 250 μm were formed using the materials shown in Tables 2-1 to 2-2.

[0149] (Examples 1-41) <Production of liquid masterbatch (F)> A liquid master batch (F-1) was prepared by kneading 10 parts of the ultraviolet absorbing dye (A-1) and 90 parts of the liquid resin (E-1) with a roll.

[0150] <Film molding> 0.5 parts of the obtained liquid master batch (F-1) was mixed with 99.5 parts of the thermoplastic resin (B-3) as the dilution resin, and the mixture was 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-41) having a thickness of 250 μm.

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

[0152] (Examples 1-59) <Production of liquid masterbatch (F)> A liquid master batch (F-19) was prepared by dispersing 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) in a bead mill.

[0153] <Film molding> 0.5 parts of the obtained liquid master batch (F-19) was mixed with 99.5 parts of the thermoplastic resin (B-3) as the dilution resin, and the mixture was 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) having a thickness of 250 μm.

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

[0155] [Appearance evaluation of molded products] It was confirmed that (X-1) to (X-77) and (Y-1) to (Y-6) were able to form uniform films. It was confirmed that (Y-7) and (Y-8) did not provide molded bodies with smooth surfaces, and are not suitable for applications requiring high molding temperatures such as engineering plastics.

[0156] [UV absorption] The transmittance of the obtained film was measured using an ultraviolet, visible and near infrared spectrophotometer (manufactured by Shimadzu Corporation) and evaluated as to whether or not it satisfied the following conditions. ◎: Light transmittance of 400 to 420 nm wavelength is less than 1% over the entire range: Good 〇: Light transmittance at wavelengths of 400 to 420 nm is less than 1% in some areas, and 1% or more in others: Practical range △: The light transmittance of the wavelength of 400 to 420 nm is 1% or more but less than 10%, and the rest is 20% or more: Not practical ×: Light transmittance of 400 to 420 nm wavelengths is 10% or more over the entire range: Not practical

[0157] [Transparency] The transparency of the obtained film was evaluated visually according to the following criteria. ○: No turbidity observed. Good △: Slight turbidity is observed. ×: Clearly turbid. Not suitable for practical use.

[0158] [Light resistance] The obtained film was measured with a xenon weather meter at 60 W / m from 300 to 400 nm. 2 The specimen was exposed to an illumination of 100 dpi for 100 hours. ○: The decrease in absorbance at the maximum absorption wavelength is less than 5% △: The decrease in absorbance at the maximum absorption wavelength is 5% or more but less than 20%. ×: The decrease in absorbance at the maximum absorption wavelength is 20% or more.

[0159] <Haze value> The haze value of the obtained film was measured with a haze meter and evaluated according to the following criteria. ◎+: Less than 0.2 Very good ◎: 0.2 or more and less than 0.5 - Very good ○: 0.5 or more but less than 2 Good △: 2 or more but 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 product of the present invention has a low transmittance per unit weight in the visible light short wavelength region of 400 to 420 nm. Since the ultraviolet absorbing dye in the resin molded product reaches a practical range even with a small amount of addition, the transparency of the film is good. In particular, compared to the resin molded product using Tinuvin 970 of the comparative example, the transparency is excellent because the ultraviolet absorbing dye reaches a practical range with a small amount of addition.

[0163] (Example 2-1) <Masterbatch manufacturing> Two parts of the ultraviolet absorbing dye (A-1) and 98 parts of the thermoplastic resin (B-1) were fed into a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) having a screw diameter of 30 mm through the same supply port, melt-kneaded at 300°C, and then cut into pellets using a pelletizer to produce a master batch (D-1).

[0164] <Film molding> 90 parts of the thermoplastic resin (B-1) of the dilution resin was mixed with 10 parts of the obtained master batch (D-1), and the mixture was melt-mixed at a temperature of 300° C. using a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.) to prepare a resin composition. The mixture was then allowed to dwell at 300° C. for 20 minutes, and then molded into a film (XX-1) having a thickness of 250 μm.

[0165] (Examples 2-2 to 2-40, Comparative Examples 2-1 to 2-8) Similarly to Example 2-1, the materials shown in Table 2 were used to form films (XX-2) to (XX-40) and (YY-1) to (YY-8) each having a thickness of 250 μm.

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

[0167] <Film molding> 0.5 parts of the obtained liquid master batch (F-1) was mixed with 99.5 parts of the thermoplastic resin (B-3) as the dilution resin, and the mixture was melt-mixed at a temperature of 300° C. using a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.) to prepare a resin composition. The mixture was then allowed to dwell at 300° C. for 20 minutes, and then molded into a film (XX-41) having a thickness of 250 μm.

[0168] (Examples 2-42 to 2-58) Similarly to Example 2-41, the materials shown in Table 2 were used to form films (XX-42) to (XX-58) having a thickness of 250 μm.

[0169] (Example 2-59) <Production of liquid masterbatch (F)> A liquid master batch (F-19) was prepared by dispersing 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) in a bead mill.

[0170] <Film molding> 0.5 parts of the obtained liquid master batch (F-19) was mixed with 99.5 parts of the thermoplastic resin (B-3) as the dilution resin, and the mixture was melt-mixed at a temperature of 300° C. using a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.) to prepare a resin composition. The mixture was then allowed to dwell at 300° C. for 20 minutes, and then molded into a film (XX-59) having a thickness of 250 μm.

[0171] (Examples 2-60 to 2-77) Similarly to Example 2-59, the materials shown in Table 2 were used to form films (XX-60) to (XX-77) having a thickness of 250 μm.

[0172] [Appearance evaluation of molded products] It was confirmed that uniform films were formed for (XX-1) to (XX-77) and (YY-1) to (YY-6). It was confirmed that (YY-7) and (YY-8) did not produce molded bodies with smooth surfaces, and are not suitable for applications requiring high molding temperatures such as engineering plastics.

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

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

[0175] 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, and therefore Table 3 lists only the results.

[0176] [Table 3]

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

Claims

1. A method for producing a transparent molded article (excluding fiber applications) for use in food packaging materials, pharmaceutical packaging materials, glass intermediate films, lenses, display materials, sensor materials, or optical control materials, comprising the steps of: a resin composition that contains an ultraviolet absorbing dye (A) that absorbs light in the ultraviolet region of less than 400 nm and in the visible light short wavelength region of 400 to 420 nm and is selected from the group consisting of the following general formulas (1), (2), and (3), and a thermoplastic resin (B), wherein 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, and the resin composition contains 0.001 to 20 mass % of the ultraviolet absorbing dye (A) in the resin composition, to prepare a master batch; Next, the master batch and the diluted resin are melt-kneaded to produce a molded body. 【Chemistry 1】 (In general formulas (1) to (3), R １ｂ ~R １ｇ , R ２ａ ~R ２ｇ , R ３ａ ~R ３ｇ each independently represents 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 , and are groups represented by the following general formulas (4-1) to (4-3). R ７ represents 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, which may have a substituent such as 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 wherein 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 via one or more -O-, -CO-, -COO-, -OCO-, -CONH-, or -NHCO-. Ar １ represents an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or a biphenyl group, which may have a substituent such as 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 addition, in the general formulas (2) to (3), R ４ , R ５ , R ６ is a hydroxyl group, R ７ Or Ar １ (wherein, in general formula (3), R ５ Or R ６ does not have a hydroxyphenyl group General formula (4-1) 【Chemistry 2】 In general formula (4-1), X １ is -CO-, -COO-, -OCO-, -CONH-, or -NHCO-. ８ is a hydrogen atom, a hydroxyl group, R ７ Or Ar １ In the formula (4-1), * represents the bonding site with the naphthalene ring of the formulae (1) to (3). General formula (4-2) 【Chemistry 3】 In general formula (4-2), X 2 , X ３ are each independently -CO-, -COO-, -OCO-, -CONH-, or -NHCO-. ９ is an arylene group having 6 to 20 carbon atoms. １０ is R ７ Or Ar １ In the formula (4-2), * represents the bonding site with the naphthalene ring of the formulae (1) to (3). General formula (4-3) 【Chemistry 4】 In general formula (4-3), X ４ , X ５ are each independently -CO-, -COO-, -OCO-, -CONH-, or -NHCO-. １１ R is a linear or branched alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. １２ is R ７ Or Ar １ n is 1 to 20. In the formula (4-3), * represents the bonding site with the naphthalene ring of the formulas (1) to (3).

2. A method for producing a molded body as described in claim 1, wherein the master batch and the diluted resin are melt-kneaded in a mass ratio of 1 / 5 to 1 / 500 to produce a molded body.

Images