WO2021132247A1

WO2021132247A1 - Resin composition and molded article

Info

Publication number: WO2021132247A1
Application number: PCT/JP2020/047977
Authority: WO
Inventors: 秋生日水; 僚一辰巳; 優美香千葉; 皓胡
Original assignee: 東洋インキＳｃホールディングス株式会社; トーヨーカラー株式会社
Priority date: 2019-12-24
Filing date: 2020-12-22
Publication date: 2021-07-01
Also published as: CN114846085B; KR20220121794A; CN114846085A

Abstract

The purpose of the present invention is to provide a resin composition that absorbs not only UV rays having a wavelength of less than 400 nm but also light in the visible light short-wavelength region having a wavelength of about 400-420 nm and that makes it possible to mold molded articles having excellent transparency. A resin composition containing: a UV-ray-absorbing pigment (A) that is a triazine compound that absorbs light in the UV region having a wavelength of less than 400 nm and light in the visible light short-wavelength region having a wavelength of 400-420 nm, the triazine compound bonding with one, two, or three naphthalene rings; and a resin.

Description

Resin composition and molded article

The present invention relates to a resin composition containing a dye and a molded product.

Conventionally, resin molded products (hereinafter referred to as molded products) have been used as packaging materials for pharmaceutical drugs and cosmetics. It is known that the organic substances contained in these packaging materials are generally deteriorated by the action of ultraviolet rays contained in sunlight and the like.

It has been pointed out that among sunlight, not only ultraviolet rays having a wavelength of less than 400 nm but also light in the visible light short wavelength region having a wavelength of about 400 to 420 nm damages organic substances and the human body. Therefore, it is effective to suppress the deterioration of the contents if the molded body contains an ultraviolet absorber that also absorbs ultraviolet rays and light in a visible light short wavelength region having a wavelength of about 400 to 420 nm. Further, the ultraviolet absorber is required to have excellent light resistance without deteriorating its properties due to exposure to ultraviolet rays over a long period of time.

Other uses of the molded body include optical applications such as a polarizing plate protective film and an antireflection film used in a liquid crystal display device, and a surface film for preventing deterioration of a light emitting element of an organic EL display device.

In the above optical applications, while there is a high temperature processing process for the composition, the molded product is required to have a high degree of dimensional stability. In particular, since the composition containing engineering plastics has a high molding temperature of, for example, 260 to 340 ° C., the ultraviolet absorber needs to have heat resistance to withstand high temperatures.

Patent Documents 1 and 2 disclose benzotriazole-based ultraviolet absorbers that absorb a short wavelength region of visible light having a wavelength of about 400 to 420 nm.

JP-A-2018-177696 Special Table 2016-514756

The conventional UV absorber has a problem that it has low heat resistance and cannot be used for a molded product of a thermoplastic resin (for example, engineering plastic) having a high melting point or a high softening point. Further, the conventional ultraviolet absorber has a low absorption coefficient per unit weight, and it is necessary to thicken the molded body in order to absorb the visible light short wavelength region. On the other hand, there is also a problem that the transparency of the molded product is lowered when the amount of the ultraviolet absorber is increased.

An object of the present invention is to provide a resin composition capable of absorbing not only ultraviolet rays having a wavelength of less than 400 nm but also light in a visible light short wavelength region having a wavelength of about 400 to 420 nm and forming a molded product having good transparency. To do.

The resin composition of the present invention absorbs light in the ultraviolet region having a wavelength of less than 400 nm and visible light in the short wavelength region having a wavelength of 400 to 420 nm, and absorbs ultraviolet light which is a triazine compound bonded to 1, 2 or 3 naphthalene rings. It is a resin composition containing a dye (A) and a thermoplastic resin (B).

According to the above invention, a resin composition capable of molding not only ultraviolet rays having a wavelength of less than 400 nm but also light in a visible light short wavelength region having a wavelength of about 400 to 420 nm and having good transparency. And a molded body can be provided.

Hereinafter, the resin composition and the molded product of the present embodiment will be described.
Unless otherwise specified, "-" indicating the numerical range shall include the lower limit value and the upper limit value.

[Resin composition]
The resin composition of the present embodiment is an ultraviolet ray which is a triazine compound which absorbs light in an ultraviolet region having a wavelength of less than 400 nm and a visible light short wavelength region having a wavelength of 400 to 420 nm and which is bonded to one, two or three naphthalene rings. It contains an absorbent dye (A) and a thermoplastic resin (B).

<Ultraviolet absorbing pigment (A)>
In the present embodiment, the ultraviolet absorbing dye (A) can absorb light in the visible light short wavelength region having a wavelength of about 400 to 420 nm in addition to the ultraviolet region having a wavelength of less than 400 nm by the action of the naphthalene ring bonded to the triazine ring. Further, the present ultraviolet absorbing dye (A) can absorb a desired wavelength with a smaller amount of addition than before. Therefore, it is possible to suppress a decrease in the transparency of the molded product. Further, the ultraviolet absorbing dye (A) has excellent heat resistance, for example, having heat resistance capable of withstanding melt kneading at 270 ° C. or higher. In the present ultraviolet absorbing dye (A), the naphthalene ring is preferably directly bonded to the triazine ring without interposing a linking group. Further, it is more preferable to have a hydroxyl group at the 2-position of at least one naphthalene ring among 1 to 3 naphthalene rings directly bonded to the triazine ring.

The ultraviolet absorbing dye (A) is preferably a compound selected from the group consisting of the following general formulas (1), general formulas (2) and general formulas (3).

(In the general formulas (1) to (3), R _1b to R _1g , R _2a to R _2g , and R _3a to R _3g are independently hydrogen atom, hydroxyl group, fluorine atom, chlorine atom, bromine atom, and iodine. It is an 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 2 to 20 carbon atoms, an alcoholic group having 1 to 20 carbon atoms, and an alkenyloxy group having 2 to 20 carbon atoms. It may have a chlorine atom, a bromine atom, an iodine atom, a nitrile group, a nitro group, a carboxyl group, or a sulfo group, and has an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and 1 to 1 carbon atoms. One or more -O-, -CO-, -COO-, -OCO-, -CONH-, or-between carbon atoms of 20 alcoholic groups and alkenyloxy groups having 2 to 20 carbon atoms. It may be connected by NHCO-.
Ar ₁ is an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a biphenyl group, and as a substituent, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms. , Aryl group with 6 to 20 carbon atoms, Arcosidel group with 1 to 20 carbon atoms, Alkoxyoxy group with 2 to 20 carbon atoms, Aryloxy group with 6 to 20 carbon atoms, Fluorine atom, Chlorine atom, Bromine atom, Iodine atom , Anitrile group, a nitro group, a carboxyl group, or a sulfo group.
Further, in the general formulas (2) to (3), R ₄ , R ₅ , and R ₆ are independently hydroxyl groups, R ₇ or Ar ₁ .

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 binding site with the naphthalene ring of the general formulas (1) to (3).

In the general formula (4-2), X ₂ and X ₃ are independently -CO-, -COO-, -OCO-, -CONH-, or -NHCO-, respectively. R ₉ is an arylene group having 6 to 20 carbon atoms. R ₁₀ is R ₇ or Ar ₁ . However, * in the general formula (4-2) represents the binding site with the naphthalene ring of the general formulas (1) to (3).

In the 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 the general formula (4-3) represents the binding site with the naphthalene ring of the general formulas (1) to (3). )

The group represented by the general formula (4-1) is preferably the group represented by the general formula (4).

In the general formula (4), Y is -NH- or -O-. R ₁₃ is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alcoholic group having 1 to 20 carbon atoms, and 2 to 20 carbon atoms. Alkenyloxy group, aryloxy group having 6 to 20 carbon atoms, fluorine atom, chlorine atom, bromine atom, iodine atom, nitrile group, nitro group, carboxyl group, or sulfo group as substituents and having 1 to 20 carbon atoms. It is an alkyl group or an aryl group having 6 to 20 carbon atoms. However, the * mark in the general formula (4) represents the binding site with the naphthalene ring in the general formulas (1) to (3).

Examples of the compound represented by the general formula (1) include the following compounds.

Examples of the compound represented by the general formula (2) include the following compounds.

Examples of the compound represented by the general formula (3) include the following compounds.

The above-mentioned method for synthesizing a 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. Another method also includes, for example, a method in which methyl 2-hydroxy-1-naphthoate and benzamidine hydrochloride are subjected to a condensation cyclization reaction using sodium methoxide. The naphthalene ring linked to the triazine ring by a single bond and the _{substituents contained in R 4} , R ₅ , and R ₆ may be introduced after the triazine structure is formed, or may be introduced before the triazine structure is formed.

The content of the ultraviolet absorbing dye (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.

<Resin>
The present resin composition contains a resin. The resin preferably contains a thermoplastic resin, a thermosetting resin, or a photocurable resin from the viewpoint of easily forming a molded product. Since this resin composition contains an ultraviolet absorbing dye (A) having excellent heat resistance, even a thermoplastic resin (B) can be preferably used, for example.

Examples of the thermoplastic resin (B) include polyolefin, polyacrylic, polyester resin, polyamide resin, polyacetal resin, polyphenylene sulfide resin, polyether ether ketone resin, cycloolefin resin, polyetherimide resin, polyamideimide resin, and polyethersulfone resin. , Polysulfone resin, polyallylate resin, polyphenylene ether resin, polycarbonate resin and the like. The thermoplastic resin (B) can be used alone or in combination of two or more.

In this resin composition, the thermoplastic resin (B) contains an ultraviolet absorbing dye (A) having excellent heat resistance, and therefore 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. Is preferably included. The melting point of the crystalline resin is more preferably 220 ° C. or higher. On the other hand, the melting point is preferably 500 ° C. or lower. The glass transition temperature of the amorphous resin is more preferably 130 ° C. or higher. On the other hand, the glass transition temperature is preferably 300 ° C. or lower. Both the melting point and the glass transition temperature can be measured with a differential scanning calorimeter, a thermogravimetric differential thermal analyzer, or the like.

Examples of the crystalline resin having a melting point of 200 ° C. or higher include polyester resin, polyamide resin, polyacetal resin, polyphenylene sulfide resin, polyetheretherketone resin and the like.
Examples of the amorphous resin having a glass transition temperature of 120 ° C. or higher include cycloolefin resin, polyetherimide resin, polyamideimide resin, polyethersulfone resin, polysulfone resin, polyarylate resin, polyphenylene ether resin, and polycardate resin. Can be mentioned.

(Polyester resin)
The polyester resin is a crystalline resin having an ester bond in the main chain of the molecule, and is a polycondensate synthesized from a dicarboxylic acid (including a derivative thereof) and a diol (dihydric alcohol or dihydric phenol); a dicarboxylic acid (dicarboxylic acid). (Including the derivative) and a polycondensation product synthesized from the cyclic ether compound; a ring-opening polymer of the cyclic ether compound and the like can be mentioned. The polyester resin may be a homopolymer composed of a polymer of a dicarboxylic acid and a diol, a copolymer using a plurality of raw materials, or a polymer blend obtained by mixing these. Examples of the derivative of the dicarboxylic acid include acid anhydrides and esterified products. The dicarboxylic acid may be either an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid, but it is preferable to contain an aromatic dicarboxylic acid from the viewpoint of improving heat resistance.

The aromatic dicarboxylic acid is, for example, terephthalic acid, isophthalic acid, phthalic acid, chlorphthalic 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, stillbenzylcarboxylic acid, diphenylbutane-p, p' -Dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, naphthalin-1,4-dicarboxylic acid, naphthalin-1,5-dicarboxylic acid, naphthalin-2,6-dicarboxylic acid, naphthalin-2,7-dicarboxylic acid, p-carboxyphenoxyacetic acid, p-carboxyphenoxybutyl acid, 1,2-diphenoxypropane-p, p'-dicarboxylic acid, 1,5-diphenoxypentane-p, p'-dicarboxylic acid, 1,6-di Phenoxyhexane-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- Examples thereof include oxypentane-p and p'-dicarboxylic acid.
Examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, adipic acid, corkic acid, mazeleic acid, sebacic acid, dodecanedicarboxylic acid, undecanedicarboxylic acid, maleic acid, fumaric acid and the like.

The dihydric alcohol is, 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. Of these, ethylene glycol, butane-1,4-diol, and cyclohexanedimethanol are preferable.
Examples of the divalent phenol include hydroquinone, resorcinol, bisphenol A and the like.
Examples of the cyclic ether compound include ethylene oxide and propylene oxide.

Dicarboxylic acid and dihydric alcohol can be used alone or in combination of two or more.

(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.

Examples of the carboxylic acid component include adipic acid, sebacic acid, isophthalic acid, terephthalic acid and the like. As the carboxylic acid component, a compound having two or more carboxyl groups can be used.
As the compound (Am) having two or more amino groups, for example, known ones can be used, for example, ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylene. Aliphatic polyamines such as tetramine; aliphatic polyamines containing alicyclic polyamines such as isophoronediamine and dicyclohexylmethane-4,4'-diamine; aromatic polyamines such as phenylenediamine and xylylenediamine; 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, Examples thereof include diaminoalcohols such as 10-triazadecane-2-ol, 3- (2-hydroxypropyl) -o-xylene-α and α'-diamine.
Examples of commercially available polyamide resins include 6 nylon (manufactured by Toray Industries, Inc.), 66 nylon (manufactured by Toray Industries, Inc.), 610 nylon and the like.

(Cycloolefin resin)
The cycloolefin resin is an amorphous resin having an alicyclic structure in the main chain and / or the side chain. Examples of the type of alicyclic structure include norbornene polymer, monocyclic cyclic olefin polymer, cyclic conjugated diene polymer, vinyl alicyclic hydrocarbon polymer, and hydrides thereof. Among these, the norbornene polymer is preferable because it is excellent in moldability and transparency. Norbornene monomers include, for example, bicyclo [2.2.1] hept-2-ene (trivial name: norbornene), tricyclo [4.3.0.12.5] deca-3,7-diene (common name: norbornene). Trivial name: dicyclopentadiene), 7,8-benzotricyclo [4.3.0.12.5] deca-3-ene (trivial name: metanotetrahydrofluorene), tetracyclo [4.4.0.12 5.17, 10] Dodeca-3-ene (trivial name: tetracyclopentadiene) and the like can be mentioned.
Examples of commercially available cycloolefin resins include Topas (manufactured by Polyplastics) and Appel (manufactured by Mitsui Chemicals).

(Polyetherimide resin)
The polyetherimide resin is an amorphous resin having a glass transition temperature of more than 180 ° C., has 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 / electronic, transportation and healthcare.
One of the processes for producing a polyetherimide resin is a polymerization of an alkali metal salt of a dihydroxyaromatic compound such as _{bisphenol A disodium salt (BPA · Na 2) 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 dihydroxyaromatic compound. The second method is to prepare bis (halophthalic anhydride) in the presence of a monofunctional compound such as phthalic anhydride that forms the terminal capping agent. Phthalic anhydride reacts with some of the organic diamines to form monohalo-bis (phthalimide). Monohalo-bis (phthalimide) acts as a terminal capping agent in the polymerization step by reaction with phenoxide end groups in the growing polymer chain.
Examples of commercially available polyetherimide resins include ULTEM (manufactured by Saudi Basic Industry Corporation).

(Polycarbonate resin)
The polycarbonate resin is an amorphous resin and is synthesized by reacting an aromatic dihydroxy compound with a carbonate precursor such as phosgene or carbonic acid diester. In the case of a synthetic reaction using phosgene, for example, an interfacial method is preferable. Further, in the case of a synthetic reaction using a carbonic acid diester, a transesterification method in which the reaction is carried out in a molten state is preferable.

Aromatic dihydroxy compounds include, for example, 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, Bis (hydroxyaryl) alkanes such as 5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1, Bis (hydroxyaryl) cycloalkanes such as 1-bis (4-hydroxyphenyl) cyclohexane 4,4'-dihydroxydiphenyl ethers, dihydroxydiaryl ethers such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl ethers, 4 , 4'-Dihydroxydiphenylsulfide, 4,4'-dihydroxy-3,3'-Dihydroxydiarylsulfides such as dimethyldiphenylsulfide, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxy-3,3 Examples thereof include dihydroxydiaryl sulfoxides such as'-dimethyldiphenyl sulfoxide, dihydroxydiaryl sulfone such as 4,4'-dihydroxydiphenyl sulfone, and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone. Further, piperazine, dipiperidyl hydroquinone, resorcin, and 4,4'-dihydroxydiphenyls may be mixed and used.

Examples of the carbonate precursor include diaryl carbonates such as phosgene, diphenyl carbonate and ditril carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

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

Commercially available polycarbonate resin products include, for example, Iupiron H-4000 (manufactured by Mitsubishi Engineering Plastics, viscosity average molecular weight 16,000), Iupiron S-3000 (manufactured by Mitsubishi Engineering Plastics, viscosity average molecular weight 23,000), and Iupiron E-2000. (Manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 27,000) and the like.

When the thermoplastic resin (B) has an appropriate melt flow rate (MFR), both fluidity and moldability can be highly compatible. The MFR of each resin is Japanese Industrial Standard JIS. It can be measured according to K 7210, and is preferably in the following range.

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 5 to 10 min at a temperature exceeding the melting point or the glass transition temperature (about 200 to 320 ° C.). 100 g / 10 min is more preferable. Hereinafter, preferable MFRs for each resin will be described.

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.

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.

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.

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.

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.

The present resin composition may contain additives in addition to the ultraviolet absorbing dye (A) and the thermoplastic resin (B). Examples of the additive include a near-infrared absorber, a light stabilizer, an antioxidant, a colorant, a wax and the like. As these additives, compounds known for molding applications can be used.

The near-infrared absorber is used to impart near-infrared absorbing ability to the molded product. 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.

The light stabilizer is used to impart UV resistance to the molded product. As the light stabilizer, for example, a hindered amine light stabilizer is preferable. The content of the light stabilizer is preferably 0.01 to 5% by mass in 100% by mass of the resin composition.

Antioxidants are used to reduce the deterioration of a molded product when it is exposed to natural light or an artificial light source and becomes hot. As the antioxidant, for example, monophenol type, bisphenol type, polymer type phenol type, sulfur type, phosphoric acid type and the like are preferable. The content of the antioxidant is preferably 0.01 to 5% by mass in 100% by mass of the resin composition.

Wax is used to more evenly disperse the UV absorbing pigment in the molded product. As the dispersant, for example, polyolefin wax, fatty acid wax, fatty acid ester wax, partially saponified fatty acid ester wax, saponified fatty acid wax and the like are preferable. The wax content is preferably 50 to 250 parts by mass with respect to 100 parts by mass of the ultraviolet absorbing dye (A).

<Manufacturing of resin composition>
Examples of the method for producing the present resin composition include a method of melt-kneading the ultraviolet absorbing dye (A) and the thermoplastic resin (B). The resin composition after melt-kneading is preferably cooled.

The melt-kneading temperature may be appropriately adjusted according to the type of the thermoplastic resin (B) used. When 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 is used as the thermoplastic resin (B), the melt kneading temperature is preferably 270 ° C. or higher, more preferably 300 ° C. or higher. .. In particular, resins such as engineering plastics having high heat resistance have low fluidity, so a processing process at a high temperature is preferable. The upper limit of the melt-kneading temperature may be a temperature at which each component does not decompose or evaporate, and is preferably 500 ° C. or lower, more preferably 450 ° C. or lower.

Examples of the melt kneading apparatus include a single-screw kneading extruder, a twin-screw kneading extruder, and a tandem twin-screw kneading extruder.

The resin composition is preferably prepared as a so-called masterbatch. When a masterbatch is prepared and then melt-kneaded with a diluting resin (thermoplastic resin (B)) to prepare a molded product, the ultraviolet absorbing dye (A) is compared with the molded product prepared without passing through the masterbatch. Can be easily uniformly dispersed in the molded product, and aggregation of the ultraviolet absorbing dye (A) can be suppressed. This improves the transparency of the molded product. The masterbatch is preferably molded into pellets using a pelletizer after the melt kneading.
When produced 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.

<Liquid masterbatch (F)>
The resin composition is prepared by preparing a liquid masterbatch (F) containing an ultraviolet absorbing dye (A) and a liquid resin (E), and then melt-kneading it together with a diluted resin (thermoplastic resin (B)). Is more preferable.

(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, more preferably 100 to 3,000 mPa · s. Within the above range, the ultraviolet absorbing dye (A) can be easily dispersed in the liquid masterbatch. The viscosity in the present specification is a value measured at 25 ° C. using a B-type viscometer according to JIS K7117-1: 1999.

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). Within this range, for example, during melt kneading, the melt viscosity can be suppressed, so that the ultraviolet absorbing dye (A) can be easily dispersed.

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 Mn200 or higher, it is easy to achieve both moldability and transparency. Further, when Mn is 2000 or less, dispersibility and antistatic property are improved.

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, polyether ester resins, and the like, but thermoplastic resins. (B) is a fatty acid polyester resin, a polyalkylene glycol resin, or a polyether ester resin in that it has high heat resistance and excellent antistatic properties even when a high molding temperature such as polyethylene terephthalate (PET) or polycarbonate is required. Is preferable.

The fatty acid polyester resin is a resin obtained by reacting an aliphatic polyvalent carboxylic acid with a polyhydric alcohol.
The aliphatic polyvalent carboxylic acid is an aliphatic carboxylic acid having two or more carboxyl groups. The aliphatic polyvalent carboxylic acid includes, for example, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecandicarboxylic acid, tricarbaryl acid, 1,3,6-hexanetricarboxylic acid, 1 , 3,5-Hextricarboxylic acids and other aliphatic polyvalent carboxylic acids and the like can be mentioned.

The polyhydric alcohol is an alcohol having two or more hydroxyl groups. Polyhydric alcohols include, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1 , 4-Butandiol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl-1 , 3-Propylenediol, 3-Methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, Examples thereof include aliphatic glycols such as 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. Be done.

Aliphatic polyvalent carboxylic acid and polyhydric alcohol can be used alone or in combination of two or more.

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

Commercially available fatty acid polyester resins include, for example, ADEKA Sizer PN-170 (made by ADEKA, viscosity 800 mPa · s at 25 ° C, freezing point -15 ° C, polyester resin adipate), ADEKA Sizer P-200 (made by ADEKA, Viscosity at 25 ° C, 2,600 mPa · s, freezing point -20 ° C, polyester resin adipate), 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.

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 at 25 ° C. of 10,000 mPa · s or less. This viscosity makes it suitable for use in liquid masterbatch applications. The alkyleneoxy group preferably has 2 to 4 carbon atoms. As a result, compatibility can be improved, while water absorption can be suppressed.

Examples of the polyether resin include polyethylene glycol having 2 carbon atoms in the repeating unit, polytrimethylene glycol and polypropylene glycol having 3 carbon atoms in the repeating unit, and all of them in the repeating unit. Examples thereof include polytetramethylene glycol and polybutylene glycol having 4 carbon atoms.

The polyether ester resin is an ester compound of an aliphatic polyvalent carboxylic acid resin and an alkylene glycol resin.
Commercially available products of the polyether ester resin include, for example, ADEKA Sizer RS-107 (manufactured by ADEKA, viscosity 20 mPa · s at 25 ° C., freezing point -47 ° C., adipic acid ether ester resin), ADEKA Sizer RS-700 (ADEKA). Co., Ltd., viscosity at 25 ° C., 30 mPa · s, freezing point-53 ° C., polyether ester resin) and the like.

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

This resin composition is produced by preparing a liquid masterbatch (F) and then melt-kneading it together with a diluting resin (thermoplastic resin (B)). Better transparency is obtained than the molded product produced from the solid masterbatch of.

Since the liquid masterbatch (F) contains the liquid resin (E) and is liquid, it has high fluidity in melt kneading with the thermoplastic resin (B) and makes the ultraviolet absorbing dye (A) very uniform. Can be dispersed. In particular, engineering plastic resins having high heat resistance have a limit in fluidity even at the melt-kneading temperature. Therefore, it is difficult to uniformly disperse due to the aggregation of the dye, and it is difficult to improve the transparency. Therefore, in the case of a thermoplastic resin (B) which 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 liquid masterbatch (F) is effective in improving transparency. In particular, it is particularly effective in applications that require high transparency, such as optical filters.

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.

(Resin type dispersant (G))
The liquid masterbatch (F) preferably contains a resin-type dispersant (G). As a result, the ultraviolet absorbing dye (A) is more uniformly dispersed in the liquid masterbatch, and the obtained molded product has higher transparency. Further, by containing the resin type dispersant (G), the storage stability of the liquid masterbatch is improved.

The resin-type dispersant (G) is a compound having an adsorption site having a property of adsorbing to an ultraviolet absorbing dye and a relaxing site compatible with a component other than the ultraviolet absorbing dye.
The resin type dispersant (G) is, for example, a polycarboxylic acid ester such as polyurethane or polyacrylate, an unsaturated polyamide, a polycarboxylic acid, a polycarboxylic acid (partial) amine salt, a polycarboxylic acid ammonium salt, or a polycarboxylic acid alkylamine. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly (lower alkyleneimine) with polyesters having free carboxyl groups, and amides thereof. Oil-based dispersants such as salts, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone and other water-soluble Examples thereof include sex resins, water-soluble polymer compounds, polyester-based materials, modified polyacrylate-based compounds, ethylene oxide / propylene oxide-added compounds, and phosphoric acid ester-based compounds.

The resin type dispersant (G) can be used alone or in combination of two or more.

Among the resin-type dispersants, a polymer dispersant having a basic functional group is preferable because the viscosity of the dispersion decreases with a small amount of addition. Further, nitrogen atom-containing graft copolymers, nitrogen atom-containing acrylic block copolymers and urethane-based polymers having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocycle, etc. in the side chain. Dispersants and the like are preferred.

The amount of the resin-type dispersant (G) used is preferably about 5 to 200% by mass, more preferably about 10 to 100% by mass, based on the film-forming property.

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, manufactured by Big Chemie Japan. 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 BYkuman, 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., EFKA-46, 47, manufactured by Ciba Japan. 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. , PB824 and the like.

When the resin type dispersant (G) is dissolved in an organic solvent, it is preferable to add the liquid resin (E), reduce the pressure and heat the mixture, and distill off the solvent before use.

<Manufacturing method of liquid masterbatch (F)>
The liquid masterbatch (F) can be produced by mixing and dispersing the ultraviolet absorbing dye (A) and the liquid resin (E). A resin-type dispersant (G) can be used in combination with the dispersion. For the dispersion, for example, a disperser such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annual bead mill, or an attritor can be used.

[Molded product]
The molded product of the present embodiment is characterized by molding a resin composition. This molded product can be produced by molding the resin composition as it is. When the resin composition is prepared as a masterbatch, a molded product can be produced by melt-kneading with a diluted resin (thermoplastic resin (B)) and then molding. The mass ratio of the masterbatch (X) to the diluted resin (Y) is preferably X / Y = 1/5 to 1/500. Within this range, the molded product can easily obtain good optical characteristics.

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% by mass in 100% by mass of the resin composition.

<Use of molded product>
The molded product can be used, for example, in food packaging materials, pharmaceutical packaging materials, displays, glass interlayer films, and lens applications.

For food packaging materials and pharmaceutical packaging materials, it is preferable to use, for example, polyester-based resin, cycloolefin-based resin, or the like as the thermoplastic resin. These molded products have improved flexibility and visibility, and can suppress deterioration of the contents.

The molded product used for displays, glass interlayer films, and lenses is preferably a film made of a resin having a transparent property with respect to a desired wavelength. Examples of the resin constituting such a molded product include polyetherimide resin, polyethersulfone resin, polyethylene terephthalate resin, polyimide resin, polysulfone resin, polyarylate resin, polyamide resin, polycarbonate resin, and alicyclic resin. Examples thereof include an olefin polymer resin having a structure (alicyclic olefin polymer resin) and a cellulose ester resin.

For display applications, this molded product is used, for example, in optical films used in televisions, personal computers, smartphones, and the like. The laminate using the molded product containing the present resin composition can suppress adverse effects on the eyes by absorbing light in a short wavelength region of ultraviolet rays and visible light contained in the backlight of the display. Further, the laminated body can suppress deterioration of the display element of the display by absorbing ultraviolet rays contained in sunlight and light in a short wavelength region of visible light.

For glass interlayer applications, this molded product is used, for example, in laminated glass used in automobiles, buildings, and the like. The laminated glass using the molded body containing the present resin composition can suppress adverse effects on the eyes and the human body by absorbing ultraviolet rays contained in sunlight and light in a short wavelength region of visible light.

In lens applications, this molded product is used, for example, in lenses used for eyeglasses, optical sensors, and the like. A lens using a molded body containing the above resin composition, for example, in a spectacle application, absorbs ultraviolet rays contained in sunlight and light in a short wavelength region of visible light to suppress adverse effects on the eyes and the human body. It is possible to increase the sensitivity of the sensor by cutting light of unnecessary wavelengths that can become noise in optical sensor applications.

This molded product also includes, for example, medical chemicals, cosmetics, food containers and packaging materials, miscellaneous goods, textile products, pharmaceutical containers, various industrial coating materials, automobile parts, home appliances, housing materials, toiletries, etc. Can be widely used for applications such as supplies. Furthermore, it can be widely used in applications such as display materials, sensor materials, and optical control materials.

Hereinafter, the present invention will be described in more detail. The present invention is not limited to the examples. Further, "parts by mass" is described as "parts", and "% by mass" is described as "%".

<Manufacturing method of ultraviolet absorbing pigment (A)>
[Ultraviolet absorbing pigment (A-1)]
170 parts of chlorobenzene, 43.4 mmol of cyanuric chloride, and 65.1 mmol of aluminum chloride were placed in a 300 mL Erlenmeyer flask, and the mixture was suspended by stirring. Next, 151.8 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 in a 500 mL beaker, and the above reaction solution was added dropwise little by little. Further, 45.0 parts of methanol was added to the Erlenmeyer flask in a plurality of times and added to a 500 mL beaker while washing. The precipitate was separated by filtration 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 sprinkled and washed with 150 parts of water. The obtained wet cake was dried at 80 ° C. overnight to obtain an ultraviolet absorbing dye (A-1).

As a result of NMR measurement of the ultraviolet absorbing dye (A-1), the result supporting the above structure was obtained. The measurement conditions are as follows.
<Measurement conditions>
Equipment: BRUKER AVANCE 400
Resonance frequency: 400MHz (1H-NMR)
Solvent: Dimethyl sulfoxide-d ₈
Tetramethylsilane was used as the internal standard substance for 1H-NMR, the chemical shift value was shown in δ value (ppm), and the coupling constant was shown in Hertz. Further, s is an abbreviation for singlet, d is an abbreviation for doublet, and m is an abbreviation 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)

As described above, the structure was identified by NMR using the ultraviolet absorbing dye (A-1) as an example. The structures of other UV-absorbing dyes were also identified by NMR in the same manner as above, but the data are omitted.

[Ultraviolet absorbing pigment (A-2)]
The ultraviolet absorbing dye (A-1) was produced in the same manner except that 1,3-dihydroxynaphthalene was added instead of 2-naphthol to obtain an ultraviolet absorbing dye (A-2).

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

[Ultraviolet absorbing pigment (A-4)]
In a 200 mL Erlenmeyer flask, 100 parts of N-methyl-2-pyrrolidone, 20.0 mmol of an ultraviolet absorbing dye (A-1), and 40.0 mmol of potassium carbonate were charged and 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 in a 1 L beaker, and the above reaction solution was added dropwise little by little. The precipitate was filtered off and sprinkled with 500 parts of water for washing. The obtained wet cake was returned to 500 parts of water, reslurried at room temperature for 30 minutes, and filtered. Then, it was sprinkled and washed with 500 parts of water. The obtained wet cake was dried at 80 ° C. overnight to obtain an ultraviolet absorbing dye (A-4).

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

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

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

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

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

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

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

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

[Ultraviolet absorbing pigment (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. , 60.0 mmol of acetyl chloride was charged with stirring, and the mixture was stirred at room temperature for 4 hours. On the other hand, 500 parts of water was charged in a 1 L beaker, and the above reaction solution was added dropwise little by little. The precipitate was filtered off and sprinkled with 500 parts of water for washing. The obtained wet cake was returned to 500 parts of water, reslurried at room temperature for 30 minutes, and filtered. Then, it was sprinkled and washed with 500 parts of water. The obtained wet cake was dried at 80 ° C. overnight to obtain an ultraviolet absorbing dye (A-12).

[Ultraviolet absorbing pigment (A-13)]
In the production of the ultraviolet absorbing dye (A-12), the ultraviolet absorbing dye (A-13) was obtained by the same method except that pivaloyl chloride was added instead of acetyl chloride.

[Ultraviolet absorbing pigment (A-14)]
In the production of the ultraviolet absorbing dye (A-1), the ultraviolet absorbing dye (A-14) was obtained by the same method except that 5-acetyl-2-naphthol was added instead of 2-naphthol.

[Ultraviolet absorbing pigment (A-15)]
In the production of the ultraviolet absorbing dye (A-1), the ultraviolet absorbing dye (A-15) was obtained by the same method except that 3-hydroxy-2-naphthoanilide was added instead of 2-naphthol.

[Ultraviolet absorbing pigment (A-16)]
In the production of the ultraviolet absorbing dye (A-1), the ultraviolet absorbing dye (A-16) was produced in the same manner except that 3-hydroxy-2'-methoxy-2-naphthanylide was added instead of 2-naphthol. Got

[Ultraviolet absorbing pigment (A-17)]
In the production of the ultraviolet absorbing dye (A-1), the ultraviolet absorbing dye was produced by the same method except that 5'-chloro-3-hydroxy-2'-methyl-2-naphthanylide was added instead of 2-naphthol. (A-17) was obtained.

[Ultraviolet absorbing pigment (A-18)]
In the production of the ultraviolet absorbing dye (A-1), the ultraviolet absorbing dye was produced by the same method except that 5'-chloro-3-hydroxy-2'-methoxy-2-naphthanylide was added instead of 2-naphthol. (A-18) was obtained.

[Ultraviolet absorbing pigment (A-19)]
In the production of the ultraviolet absorbing dye (A-1), the ultraviolet absorbing dye (A-19) was produced by the same method except that 3-hydroxy-3'-nitro-2-naphthanylide was added instead of 2-naphthol. Got

[Ultraviolet absorbing pigment (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 with stirring, and 4 at room temperature. Stirred for hours. On the other hand, 500 parts of water was charged in a 1 L beaker, and the above reaction solution was added dropwise little by little. The precipitate was filtered off and sprinkled with 500 parts of water for washing. The obtained wet cake was returned to 500 parts of water, reslurried at room temperature for 30 minutes, and filtered. Then, it was sprinkled and washed with 500 parts of water. The obtained wet cake was dried at 80 ° C. overnight to obtain an ultraviolet absorbing dye (A-20).

[Ultraviolet absorbing pigment (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 Co., Ltd.) were charged and 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 in a 1 L beaker, and the above reaction solution was added dropwise little by little. The precipitate was filtered off and sprinkled with 500 parts of water for washing. The obtained wet cake was returned to 500 parts of water, reslurried at room temperature for 30 minutes, and filtered. Then, it was sprinkled and washed with 500 parts of water. The obtained wet cake was dried at 80 ° C. overnight to obtain an ultraviolet absorbing dye (A-21).

[Ultraviolet absorbing pigment (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 Co., Ltd.) were charged and 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 in a 1 L beaker, and the above reaction solution was added dropwise little by little. The precipitate was filtered off and sprinkled with 500 parts of water for washing. The obtained wet cake was returned to 500 parts of water, reslurried at room temperature for 30 minutes, and filtered. Then, it was sprinkled and washed with 500 parts of water. The obtained wet cake was dried at 80 ° C. overnight to obtain an ultraviolet absorbing dye (A-22).

[Ultraviolet absorbing pigment (A-23)]
In the production of UV absorbing dye (A-22), ω-carboxypolycaprolactone (n≈2) monoacrylate instead of 2-methacryloyloxyethyl succinic acid (light ester HO-MS (N), manufactured by Kyoeisha Chemical Co., Ltd.) It was produced in the same manner except that (Aronix M-5300, manufactured by Toagosei Co., Ltd.) was added to obtain an ultraviolet absorbing dye (A-23).

[Ultraviolet absorbing pigment (A-24)]
In the production of UV absorbing dye (A-22), monohydroxyethyl phthalate (Aronix M-5400, Toa) was used instead of 2-methacryloyloxyethyl succinic acid (light ester HO-MS (N), manufactured by Kyoeisha Chemical Co., Ltd.). It was produced in the same manner except that (manufactured by Synthetic Co., Ltd.) was added to obtain an ultraviolet absorbing dye (A-24).

[Ultraviolet absorbing pigment (A-25)]
In a 300 mL 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 stirred. Suspended. Next, 65.1 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 in a 500 mL beaker, and the above reaction solution was added dropwise little by little. Further, 45.0 parts of methanol was added to the Erlenmeyer flask in a plurality of times and added to a 500 mL beaker while washing. The precipitate was separated by filtration 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 sprinkled and washed with 150 parts of water. The obtained wet cake was dried at 80 ° C. overnight to obtain an ultraviolet absorbing dye (A-25).

[Ultraviolet absorbing pigment (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 placed in a 300 mL Erlenmeyer flask and suspended by stirring. 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 in a 500 mL beaker, and the above reaction solution was added dropwise little by little. Further, 45.0 parts of methanol was added to the Erlenmeyer flask in a plurality of times and added to a 500 mL beaker while washing. The precipitate was separated by filtration 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 sprinkled and washed with 150 parts of water. The obtained wet cake was dried at 80 ° C. overnight to obtain an ultraviolet absorbing dye (A-26).

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

[Manufacture of UV Absorbent Dye (A-28) 1 (A-28-1)]
In the production of UV absorbing dye (A-25), 2-chloro-4,6-diphenyl-1 instead of 2-chloro-4,6-di (naphthalene-1-yl) -1,3,5-triazine , 3,5-Triazine was added, and the mixture was produced in the same manner to obtain an ultraviolet absorbing dye (A-28).

[Manufacture of UV Absorbent Dye (A-28) 2 (A-28-2)]
Methyl 2-hydroxy-1-naphthoate was charged in a 500 mL Erlenmeyer flask in an amount of 420 mmоl and heated to 90 ° C. with stirring. Next, 26 parts of a 30% solution of 128 mmоl of benzoamidine hydrochloride and sodium methylate was charged, and the mixture was stirred at 90 ° C. for 22 hours. Then, 200 parts of methanol was 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, it was sprinkled and washed with 150 parts of methanol. The obtained wet cake was dried at 80 ° C. overnight to obtain an ultraviolet absorbing dye (A-28). As described above, the ultraviolet absorbing dye (A-28) of Production 2 synthesized the same compound (A-28) by a synthetic route different from that of Production 1.

[Ultraviolet absorbing dye (A-29)]
In the production of the ultraviolet absorbing dye (A-28-2), the ultraviolet absorbing dye (A-29) was obtained by the same method except that p-methylbenzoamidine hydrochloride was added instead of the benzoamidine hydrochloride. It was.

[Ultraviolet absorbing pigment (A-30)]
In the production of the ultraviolet absorbing dye (A-28-2), the ultraviolet absorbing dye (A-30) was obtained by the same method except that p-butoxybenzoamidine hydrochloride was added instead of benzoamidine hydrochloride. It was.

[Ultraviolet absorbing pigment (A-31)]
In the production of UV absorbing dye (A-25), 2-chloro-4,6-dimethoxy-1 instead of 2-chloro-4,6-di (naphthalene-1-yl) -1,3,5-triazine , 3,5-Triazine was added, but the same method was used to obtain an ultraviolet absorbing dye (A-31).

[Ultraviolet absorbing pigment (A-32)]
In the production of UV-absorbing dye (A-25), 2,4-bis [4- (tert-) instead of 2-chloro-4,6-di (naphthalene-1-yl) -1,3,5-triazine Butyl) phenyl] -6-chloro-1,3,5-triazine was added, but the mixture was produced in the same manner to obtain an ultraviolet absorbing dye (A-32).

[Ultraviolet absorbing pigment (A-33)]
In the production of UV absorbing dye (A-25), 2-([1,1'-biphenyl] instead of 2-chloro-4,6-di (naphthalene-1-yl) -1,3,5-triazine] It was produced in the same manner except that -4-yl) -4-chloro-6-phenyl-1,3,5-triazine was added to obtain an ultraviolet absorbing dye (A-33).

[Absorbance measurement]
(Test Examples 1 to 35, Comparative Test Examples 1 to 6)
Table 1 shows the results of measuring the ultraviolet to visible absorption spectra of the ultraviolet absorbing dyes (A-1) to (A-33) and the following comparative dyes (AA-1) to (AA-3). .. The following ultraviolet absorber was used as the comparative dye. All of these ultraviolet absorbers were evaluated for visible light absorption and the like after confirming that the transmittance was less than 10% in the wavelength range of 320 nm or more and less than 400 nm.

(AA-1) Tinuvin970 (Boztriazole UV absorber manufactured by BASF Japan Ltd.)
(AA-2) Tinuvin 460 (BASF Japan, triazine-based UV absorber)
(AA-3) LA-F70 (ADEKA, triazine-based UV absorber)

(AA-1) is a benzotriazole-based ultraviolet absorber, which is different from the structure of the present invention. (AA-2) and (AA-3) are triazine-based ultraviolet absorbers, each of which does not have a naphthalene ring.

The solution preparation method for absorbance measurement and the measurement conditions are as follows.

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

The UV absorbers of the UV absorbing dyes (A-2) to (A-33) and the comparative dyes (AA-1) to (AA-3) were also prepared so as to have the concentrations shown in Table 1.

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

The evaluation criteria for the ultraviolet to visible absorption spectrum are as follows.
⊚: Absorption of wavelength 400 to 420 nm is 0.3 or more over the entire region: Good 〇: Absorption of wavelength 400 to 420 nm is partly 0.3 or more, others are less than 0.3: Practical range Δ: Wavelength 400 to 420 nm Absorptivity is partly 0.1 or more and less than 0.3, others less than 0.1: Not practical ×: Absorptivity at wavelengths of 400 to 420 nm is less than 0.1 over the entire region: Not practical

As shown in Table 1, the ultraviolet absorbing dye (A) used in the resin composition of the present invention has visible light having a wavelength of 400 to 420 nm as compared with the ultraviolet absorbing agent (AA) used in the conventional resin composition. It can be seen that the absorbance per unit weight is high in the short wavelength region.

<Thermoplastic resin (B)>
(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) Iupiron S-3000 (polycarbonate resin, manufactured by Mitsubishi Engineering Plastics, 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, 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, amorphous resin, glass transition temperature 135 ° C, MFR 11 g / 10 min or more (260 ° C / 2.16 kg))
(B-5) Amylan 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 Industry Corporation, amorphous resin, glass transition temperature 217 ° C, MFR 8 g / 10 min or more (337 ° C / 6.6 kg))

<Liquid resin (E)>
(E-1): Uniol 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): Uniol 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 (made by ADEKA, ether ester resin, adipic acid ether ester resin, number average molecular weight 430, viscosity 20 mPa · s)
(E-5): ADEKA Sizer RS-700 (made by ADEKA, ether ester resin, number average molecular weight 550, viscosity 30 mPa · s)
(E-6): ADEKA Sizer PN-250 (manufactured by ADEKA, polyester resin of fatty acid, polyester resin of adipic acid, number average molecular weight 2100, viscosity 4,500 mPa · s)
(E-7): ADEKA Sizer PN-350 (manufactured by ADEKA, fatty acid polyester resin, adipic acid polyester resin, number average molecular weight 4500, viscosity 10,000 mPa · s)

<Resin type dispersant (G)>
(Manufacturing of resin type dispersant solution (G-1))
By adding the same amount of liquid resin (E-4) as BYK-LPN6919 to BYK-LPN6919 manufactured by Big Chemie Japan, which has a non-volatile content of 60%, heating to 100 ° C. and reducing the pressure to distill off the solvent. A resin-type dispersant solution (G-1) having a non-volatile content / liquid resin (E-4) = 1/1 of BYK-LPN6919 was obtained.

[Synthesis of ethylenically unsaturated monomer (b-5)]
60 parts of 2-isocyanatoethyl methacrylate, 29 parts of 3- (dimethylamino) propylamine, and 120 parts of tetrahydrofuran (THF) were charged in a reaction vessel equipped with a stirrer and a thermometer, and the mixture was stirred at room temperature for 5 hours. After confirming that the reaction was completed 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%). Identification of the obtained compound was carried out by 1H-NMR.

[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 synthesizing the ethylenically unsaturated monomer (b-5) and ion-exchanged water After charging 5 parts and stirring at room temperature, 8 parts of a 35% aqueous hydrochloric acid solution was added dropwise. It was confirmed by the amine value measurement that the reaction was completed, and 20 parts of an aqueous ethylenically unsaturated monomer (b-9) was obtained as a pale yellow transparent liquid. Identification of the obtained compound was carried out by 1H-NMR.

(Manufacturing of resin type dispersant solution (G-2))
In a reaction vessel equipped with a gas introduction 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 50 parts were flowed with nitrogen. The mixture was stirred at ° C. for 1 hour, 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 non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, in this reaction vessel, 20 parts of PGMAc, 21.2 parts of an ethylenically unsaturated monomer (b-5) as a second block monomer, and 27 parts of an aqueous ethylenically unsaturated monomer (b-9) (nonvolatile). (38%) was added, and the mixture was stirred while maintaining the atmosphere of 110 ° C. and nitrogen, and the reaction was continued. 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 in terms of the non-volatile content, and the reaction solution was cooled to room temperature to stop the polymerization. did.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by mass. In this way, a resin-type dispersant solution having an amine value of 50 mgKOH / g per non-volatile content, 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. It was.
Further, the same amount of liquid resin (E-4) as the non-volatile content of this resin-type dispersant solution is added, heated to 100 ° C. and depressurized to distill off PGMAc and water to obtain this resin-type dispersant solution. A resin-type dispersant solution (G-2) having a non-volatile content / liquid resin (E-4) = 1/1 was obtained.

(Example 1-1)
<Manufacturing of masterbatch>
Two parts of the ultraviolet absorbing dye (A-1) and 98 parts of the thermoplastic resin (B-1) are put into a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) with a screw diameter of 30 mm from the same supply port and melted at 300 ° C. After kneading, a master batch (D-1) was prepared by cutting into pellets using a pelletizer.

<Film molding>
10 parts of the obtained masterbatch (D-1) was mixed with 90 parts of the thermoplastic resin (B-1) of the diluted resin, and the temperature was 300 ° C. using a T-die molding machine (manufactured by Toyo Seiki). A film (X-1) having a thickness of 250 μm was formed by melting and mixing with.

(Examples 1-2 to 1-40, Comparative Examples 1-1 to 1-6)
Similar to Example 1-1, the films (X-2) to (X-40) and (Y-1) to (Y-) having a thickness of 250 μm were used using the materials shown in Tables 2-1 to 2-2. 6) was molded.

(Example 1-41)
<Manufacturing of liquid masterbatch (F)>
A liquid masterbatch (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.

<Film molding>
0.5 parts of the obtained liquid masterbatch (F-1) was mixed with 99.5 parts of the thermoplastic resin (B-3) of the diluted resin, and a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.) was used. Then, the film (X-41) having a thickness of 250 μm was formed by melting and mixing at a temperature of 300 ° C.

(Examples 1-42 to 1-58)
In the same manner as in 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.

(Example 1-59)
<Manufacturing of liquid masterbatch (F)>
A liquid masterbatch (F-19) is prepared by dispersing 10 parts of an ultraviolet absorbing dye (A-1), 20 parts of a resin type dispersant (G-1), and 70 parts of a liquid resin (E-1) with a bead mill. Made.

<Film molding>
0.5 parts of the obtained liquid masterbatch (F-19) was mixed with 99.5 parts of the thermoplastic resin (B-3) of the diluted resin, and a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.) was used. Using, melt-mixed at a temperature of 300 ° C. to form a film (X-59) having a thickness of 250 μm.

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

[Appearance evaluation of molded product]
Regarding (X-1) to (X-77) and (Y-1) to (Y-6), it was confirmed that a uniform film was formed.

[UV absorption]
The transmittance of the obtained film was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation), and it was evaluated whether or not the following conditions were satisfied.
⊚: Light transmittance at a wavelength of 400 to 420 nm is less than 1% over the entire region: Good 〇: Light transmittance at a wavelength of 400 to 420 nm is partially less than 1%, others are 1% or more: Practical range Δ: Wavelength 400 to 420 nm Light transmittance is partly 1% or more and less than 10%, others are 20% or more: Not practical ×: Light transmittance of wavelength 400 to 420 nm is 10% or more over the entire region: Not practical

[Transparency] The transparency of the obtained film was visually evaluated. The evaluation criteria are as follows.
◯: No turbidity is observed. Good Δ: Some turbidity is observed. Practical range ×: Clearly turbidity is observed. Impractical

[Light resistance]
The obtained film was exposed to light having a wavelength of 300 to 400 nm with an illuminance of 60 W / m ² for 100 hours using a xenon weather meter.
〇: Absorbance reduction rate of maximum absorption wavelength is less than 5% Δ: Absorbance reduction rate of maximum absorption wavelength is 5% or more, less than 20% ×: Absorbance reduction rate of maximum absorption wavelength is 20% or more

<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 〇: 0.5 or more and less than 2 Good △: 2 or more and less than 5 Good ×: 5 or more Not practical

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 having a wavelength of 400 to 420 nm. Since a small amount of the ultraviolet absorbing dye in the resin molded product is added to reach a practical range, the transparency of the film is good. In particular, as compared with the resin molded product using Tinuvin 970 of the comparative example, the addition of a small amount reaches a practical range, so that the transparency is excellent.

(Example 2-1)
<Manufacturing of masterbatch>
Two parts of the ultraviolet absorbing dye (A-1) and 98 parts of the thermoplastic resin (B-1) are put into a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) with a screw diameter of 30 mm from the same supply port and melted at 300 ° C. After kneading, a master batch (D-1) was prepared by cutting into pellets using a pelletizer.

<Film molding>
10 parts of the obtained masterbatch (D-1) was mixed with 90 parts of the thermoplastic resin (B-1) of the diluted resin, and the temperature was 300 ° C. using a T-die molding machine (manufactured by Toyo Seiki). A resin composition was prepared by melting and mixing with. Then, after allowing the film (XX-1) to stay at 300 ° C. for 20 minutes, a film (XX-1) having a thickness of 250 μm was formed.

(Examples 2-2 to 2-40, Comparative Examples 2-1 to 2-6)
In the same manner as in Example 2-1 using the materials shown in Table 2, films (XX-2) to (XX-40) and (YY-1) to (YY-6) having a thickness of 250 μm were formed.

(Example 2-41)
<Manufacturing of liquid masterbatch (F)>
A liquid masterbatch (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.

<Film molding>
0.5 parts of the obtained liquid masterbatch (F-1) was mixed with 99.5 parts of the thermoplastic resin (B-3) of the diluted resin, and a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.) was used. A resin composition was prepared by melting and mixing at a temperature of 300 ° C. Then, after allowing the film to stay at 300 ° C. for 20 minutes, a film (XX-41) having a thickness of 250 μm was formed.

(Examples 2-42 to 2-58)
Similar to Example 2-41, films (XX-42) to (XX-58) having a thickness of 250 μm were formed using the materials shown in Table 2.

(Example 2-59)
<Manufacturing of liquid masterbatch (F)>
A liquid masterbatch (F-19) is prepared by dispersing 10 parts of an ultraviolet absorbing dye (A-1), 20 parts of a resin type dispersant (G-1), and 70 parts of a liquid resin (E-1) with a bead mill. Made.

<Film molding>
0.5 parts of the obtained liquid masterbatch (F-19) was mixed with 99.5 parts of the thermoplastic resin (B-3) of the diluted resin, and a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.) was used. A resin composition was prepared by melting and mixing at a temperature of 300 ° C. Then, after allowing the film to stay at 300 ° C. for 20 minutes, a film (XX-59) having a thickness of 250 μm was formed.

(Examples 2-60 to 2-77)
Similar to Example 2-59, films (XX-60) to (XX-77) having a thickness of 250 μm were formed using the materials shown in Table 2.

[Appearance evaluation of molded product]
Regarding (XX-1) to (XX-77) and (YY-1) to (YY-6), it was confirmed that a uniform film was formed.

[Heat-resistant]
Examples (1-1) to (1-77) and Comparative Example (1-1) were used for the obtained films (XX-1) to (XX-77) and (YY-1) to (YY-8). The difference in ultraviolet absorption between the films (X-1) to (X-40) and (Y-1) to (Y-8) obtained in (1-8) was compared and evaluated. The evaluation criteria are as follows.
⊚: Difference in light transmittance at wavelength 400 to 420 nm is less than 1%: Good 〇: Difference in light transmittance at wavelength 400 to 420 nm is less than 5%: Practical range Δ: Difference in light transmittance at wavelength 400 to 420 nm Less than 10%: Not practical ×: Difference in light transmittance between wavelengths of 400 to 420 nm is 10% or more: Not practical

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. Therefore, only the results are shown in Table 3.

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

The thermoplastic resins used in Examples 3 to 7 below (all having a number average molecular weight of 30,000 or more) are shown below.
(C-1) Polyethylene (Suntech LD M2270, MFR = 7g / 10min, manufactured by Asahi Kasei Chemicals Co., Ltd.)
(C-2) Polyethylene (Novatec UJ790, MFR = 50g / 10min, manufactured by Japan Polyethylene Corporation)
(C-3) Polypropylene (Novatec PP FA3EB, MFR = 10.5g / 10min, manufactured by Japan Polypropylene Corporation)
(C-4) Polypropylene (Prime Polypro J226T, MFR = 20g / 10min, manufactured by Prime Polymer Co., Ltd.)
(H-1) Polycarbonate (Iupilon S3000, MFR = 15g / 10min, manufactured by Mitsubishi Engineering Plastics)
(H-2) Polymethacrylic resin (Acrypet MF, MFR = 14g / 10min, manufactured by Mitsubishi Rayon)
(H-3) Polyester (Mitsui Pet SA135, manufactured by Mitsui Chemicals, Inc.)
(H-4) Cycloolefin resin (TOPAS5013L-10, manufactured by Mitsui Chemicals, Inc.)
(H-5) Polyvinyl butyral resin (Mobital B20H, manufactured by Kuraray)

The liquid resin used in the examples is shown below.
(I-1) Uniol D-400 (manufactured by NOF CORPORATION, polyalkylene glycol resin, polypropylene glycol resin, number average molecular weight 400, viscosity 100 mPa · s)
(I-2) ADEKA Sizer RS-107 (made by ADEKA, ether ester resin, adipic acid ether ester resin, number average molecular weight 430, viscosity 20 mPa · s)
(I-3) ADEKA Sizer PN-6810 (manufactured by ADEKA, tributyl acetylcitrate, number average molecular weight 190, viscosity 43 mPa · s)
(I-4) ADEKA Sizer PN-250 (manufactured by ADEKA, aliphatic polyester resin, polyester resin with adipic acid, number average molecular weight 2100, viscosity 4,500 mPa · s)

The plasticizer used in the examples is shown below.
(J-1) Triethylene Glycol-Di-2-Ethylhexanoate (J-2) Triethylene Glycol-Di-n-Heptanoate

<Resin type dispersant (K)>
(Manufacturing of resin type dispersant solution (K-1))
Add the same amount of liquid resin (I-2) as the non-volatile content of BYK-LPN6919 to BYK-LPN6919 manufactured by Big Chemie Japan, which has a non-volatile content of 60%, heat to 100 ° C. and reduce the pressure to distill off the solvent. As a result, a resin-type dispersant solution (K-1) having a non-volatile content / liquid resin (I-2) = 1/1 of BYK-LPN6919 was obtained.

(Manufacturing of resin type dispersant solution (K-2))
Add the same amount of liquid resin (I-2) as the non-volatile content of Disperbyk-2000 to Disperbyk-2000 manufactured by Big Chemie Japan Co., Ltd., which has a non-volatile content of 40%, heat to 100 ° C., reduce the pressure, and distill off the solvent. As a result, a non-volatile component / liquid resin (I-2) = 1/1 resin-type dispersant solution K-2) of Disperbyk-2000 was obtained.
(Example 3-1)
[Manufacturing of masterbatch]
Two parts of the ultraviolet absorbing dye (A-1) and 100 parts by mass of the polyolefin (C-1) are put into a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) with a screw diameter of 30 mm from the same supply port, and melt-mixed at 240 ° C. After smelting, it was cut into pellets using a pelletizer to prepare a masterbatch.

[Film molding]
10 parts by mass of the obtained masterbatch and 100 parts by mass of polyolefin (C-1) as a diluent were mixed. Next, using a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.), melt mixing was performed at a temperature of 180 ° C. and molding was performed to obtain a film having a thickness of 250 μm.

(Examples 3-2 to 3-38, Comparative Examples 3-1 to 3-6)
A masterbatch was produced in the same manner as in Example 3-1 except that the materials of Example 3-1 were changed to the materials and blending amounts shown in Table 4, and then Examples 3-2 to 3-38, Comparative Example. Films 3-1 to 3-6 were produced, respectively.

[Visible light absorption]
The transmittance of the obtained film was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation), and it was evaluated whether or not the following conditions were satisfied.
⊚: Light transmittance at a wavelength of 400 to 420 nm is less than 1% over the entire region: Good 〇: Light transmittance at a wavelength of 400 to 420 nm is partially less than 1%, others are 1% or more: Practical range Δ: Wavelength 400 to 420 nm Light transmittance is partly 1% or more and less than 10%, others are 20% or more: Not practical ×: Light transmittance of wavelength 400 to 420 nm is 10% or more over the entire region: Not practical

As shown in Table 4, the ultraviolet absorbing dye of the present invention has a low transmittance per unit weight in the visible light short wavelength region having a wavelength of 400 to 420 nm. It was found that the transparency of the film was not impaired because the addition of a small amount reached a practical range. In particular, it was found that a small amount of addition reached a practical range as compared with Tinuvin 970 of the comparative example.

(Example 4-1)
(Manufacturing of masterbatch)
100 parts of polycarbonate (H-1) and 2 parts of ultraviolet absorbing dye (A-1) are put into a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) with a screw diameter of 30 mm from the same supply port and melt-kneaded at 280 ° C. Then, it was cut into pellets using a pelletizer to prepare a composition (master batch).
(Film molding)
10 parts of the obtained composition was mixed with 100 parts of the diluted resin polycarbonate (H-1), and melt-mixed at a temperature of 280 ° C. using a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.) to obtain a thickness. A 250 μm film was molded.

(Examples 4-2 to 4-8, Comparative Examples 4-1 to 4-6)
A masterbatch was produced in the same manner as in Example 4-1 except that the materials of Example 4-1 were changed to the materials and blending amounts shown in Table 5-1 and then Examples 4-2 to 4-8. , Comparative Examples 4-1 to 4-6 were produced, respectively.

(Example 4-9)
(Manufacturing of masterbatch)
100 parts of polymethacrylic resin (H-2) and 2 parts of ultraviolet absorbing dye (A-1) are put into a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) with a screw diameter of 30 mm from the same supply port and melted at 240 ° C. After kneading, the composition (master batch) was prepared by cutting into pellets using a pelletizer.
(Film molding)
10 parts of the obtained composition was mixed with 100 parts of the methacrylic resin (H-2) of the diluted resin, melt-mixed at a temperature of 280 ° C. using a T-die molding machine (manufactured by Toyo Seiki), and thickened. A 250 μm T-die film was formed.

(Examples 4-10 to 4-16)
A masterbatch was produced in the same manner as in Example 4-9, except that the materials of Example 4-9 were changed to the materials and blending amounts shown in Table 5-1 and then Examples 4-10-4-16. Films were manufactured respectively.

(Example 4-17)
(Manufacturing of masterbatch)
100 parts of polyester (H-3) and 2 parts of ultraviolet absorbing dye (A-1) are put into a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) with a screw diameter of 30 mm from the same supply port and melt-kneaded at 280 ° C. Then, it was cut into pellets using a pelletizer to prepare a composition (master batch).
(Film molding)
10 parts of the obtained composition was mixed with 100 parts of the diluted resin polyester (H-3), and melt-mixed at a temperature of 280 ° C. using a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.) to obtain a thickness. A 250 μm film was molded.

(Examples 4-18 to 4-24)
A masterbatch was produced in the same manner as in Example 4-17, except that the materials of Example 4-17 were changed to the materials and blending amounts shown in Table 5-1 and then Examples 4-18 to 4-24. Films were manufactured respectively.

(Example 4-25)
(Manufacturing of masterbatch)
100 parts of cycloolefin resin (H-4) and 2 parts of ultraviolet absorbing dye (A-1) are put into a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) with a screw diameter of 30 mm from the same supply port and melted at 240 ° C. After kneading, the composition (master batch) was prepared by cutting into pellets using a pelletizer.
(Film molding)
10 parts of the obtained composition was mixed with 100 parts of the diluted resin cycloolefin resin (H-4), and melt-mixed at a temperature of 280 ° C. using a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.). A T-die film having a thickness of 250 μm was formed.

(Examples 4-26 to 4-32)
A masterbatch was produced in the same manner as in Example 4-25, except that the materials of Example 4-25 were changed to the materials and blending amounts shown in Table 5-1 and then Examples 4-26 to 4-32. Films were manufactured respectively.

(Example 4-33)
(Manufacturing of masterbatch)
100 parts of polyvinyl butyral resin (H-5) and 2 parts of ultraviolet absorbing dye (A-1) are put into a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) with a screw diameter of 30 mm from the same supply port and melted at 240 ° C. After kneading, the composition (master batch) was prepared by cutting into pellets using a pelletizer.
(Film molding)
10 parts of the obtained composition was mixed with 100 parts of the diluted resin polyvinyl butyral resin (H-5), and melt-mixed at a temperature of 280 ° C. using a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.). A T-die film having a thickness of 250 μm was formed.

(Examples 4-34 to 4-40)
A masterbatch was produced in the same manner as in Example 4-25, except that the materials of Example 4-33 were changed to the materials and blending amounts shown in Table 5-1 and then Examples 4-34-4-40. Films were manufactured respectively.

(Example 4-41)
(Manufacturing of liquid masterbatch)
A liquid masterbatch was prepared by kneading 10 parts of the ultraviolet absorbing dye (A-1) and 90 parts of the liquid resin (I-1) with a roll.
(Film molding)
Two parts of the obtained liquid masterbatch are mixed with 98 parts of the diluted resin polycarbonate (H-1), melt-mixed at a temperature of 280 ° C. using a T-die molding machine (manufactured by Toyo Seiki), and thickened. A 250 μm T-die film was formed.

(Examples 4-42 to 82)
A liquid masterbatch was produced using the materials shown in Table 5-2 in the same manner as in Example 4-41, and then the films of Examples 4-42 to 4-82 were produced, respectively.

(Example 4-83)
(Manufacturing of plasticizer dispersion)
A plasticizer dispersion was prepared by bead-dispersing 10 parts of the ultraviolet absorbing dye (A-1) and 90 parts of the plasticizer (J-1).
(Film molding)
Two parts of the obtained plasticizer dispersion was mixed with 98 parts of the diluted resin polycarbonate (H-1), and melt-mixed at a temperature of 280 ° C. using a T-die molding machine (manufactured by Toyo Seiki). A T-die film having a thickness of 250 μm was formed.

(Examples 4-84 to 4-122)
In the same manner as in Example 4-83, the plasticizer dispersion was prepared using the materials shown in Table 5-3, and then the films of Examples 4-84 to 4-122 were produced, respectively.

[Light resistance]
The obtained film was exposed to light having a wavelength of 300 to 400 nm with an illuminance of 60 W / m ² for 100 hours using a xenon weather meter.
〇: Absorbance reduction rate of maximum absorption wavelength is less than 5% Δ: Absorbance reduction rate of maximum absorption wavelength is 5% or more, less than 20% ×: Absorbance reduction rate of maximum absorption wavelength is 20% or more)

As shown in Tables 5-1 to 5-3, the ultraviolet absorbing dye (A) has a low transmittance per unit weight in the visible light short wavelength region having a wavelength of 400 to 420 nm. It was found that the transparency of the film was not impaired because the addition of a small amount reached a practical range. In particular, it was found that a small amount of addition reached a practical range as compared with Tinuvin 970 of the comparative example.

(Production Example K-1 of Adhesive Resin)
Using a reactor equipped with a stirrer, reflux cooler, nitrogen introduction tube, thermometer, and dropping tube, 96.0 parts of n-butyl acrylate and 4.0 parts of 2-hydroxyl ethyl acrylate under a nitrogen atmosphere. 50% of the total amount, 0.2 parts of 2,2'-azobisisobutylnitrile as the polymerization initiator, and 150 parts of ethyl acetate as the solvent were charged into the reaction vessel, and the remaining 50% of the total amount and an appropriate amount. Ethyl acetate was charged into the dropping tank. Next, heating is started to confirm the start of the reaction in the reaction vessel, and then, under reflux, the contents of the dropping tube and 0.01 part of 2,2'-azobisisobutynitrile diluted ethyl acetate are added. Dropped. After completion of the dropping, the reaction was carried out for 5 hours while maintaining the reflux state. After completion of the reaction, the mixture was cooled and an appropriate amount of ethyl acetate was added to obtain Production Example K-1 of an adhesive resin which is an acrylic resin. The weight average molecular weight of the pressure-sensitive adhesive resin of Production Example K-1 obtained was 500,000, the non-volatile content was 40%, and the viscosity was 3,200 mPa · s.

(Manufacturing example of adhesive resin K-2)
Using a reactor equipped with a stirrer, reflux cooler, nitrogen introduction tube, thermometer, and dropping tube, the total amount of n-butyl acrylate 96.0 parts and acrylic acid 4.0 parts under a nitrogen atmosphere. 50% of this, 0.2 parts of 2,2'-azobisisobutylnitrile as a polymerization initiator, and 150 parts of ethyl acetate as a solvent were charged into the reaction vessel, and the remaining 50% of the total amount and an appropriate amount of ethyl acetate were charged. Was charged into the dropping tank. Next, heating is started to confirm the start of the reaction in the reaction vessel, and then, under reflux, the contents of the dropping tube and 0.01 part of 2,2'-azobisisobutynitrile diluted ethyl acetate are added. Dropped. After completion of the dropping, the reaction was carried out for 5 hours while maintaining the reflux state. After completion of the reaction, the mixture was cooled and an appropriate amount of ethyl acetate was added to obtain Production Example K-2 of an adhesive resin which is an acrylic resin. The weight average molecular weight of the pressure-sensitive adhesive resin of Production Example K-2 obtained was 600,000, the non-volatile content was 40%, and the viscosity was 4,000 mPa · s.

(Example 5-1)
As the adhesive resin, 0.2 part of the ultraviolet absorbing dye (A-1) was mixed with 100 parts of the non-volatile content of the adhesive resin of Production Example K-1, and KBM-403 (Shin-Etsu Chemical Co., Ltd.) was used as a silane coupling agent. Add 0.1 part of (industrial) and 0.4 part of trimethylolpropan adduct of tolylene diisocyanate (abbreviation: TDI-TMP, NCO value = 13.2, non-volatile content = 75%) as a curing agent, and stir well. I got the adhesive. Then, this adhesive was applied on a release film of a polyethylene terephthalate base material having a thickness of 38 μm so as to have a thickness of 50 μm after drying, and dried in a hot air oven at 100 ° C. for 2 minutes. Then, a 25 μm polyethylene terephthalate film was attached to the pressure-sensitive adhesive layer side and aged in this state at room temperature for 7 days to obtain a pressure-sensitive adhesive sheet.

(Examples 5-2 to 5-7, Comparative Examples 5-1 to 5-2)
As shown in Table 6, the adhesive sheets of Examples 5-2 to 5-7 and Comparative Examples 5-1 to 5-2 were obtained in the same manner as in Example 5-1.

(Evaluation of adhesive sheet)
(1) Adhesive Strength The obtained adhesive sheet was prepared to have a width of 25 mm and a length of 150 mm. In an atmosphere of 23 ° C. and 50% relative humidity, the peelable film was peeled off from the pressure-sensitive adhesive sheet, the exposed pressure-sensitive adhesive layer was attached to a glass plate, and pressure-bonded once with a 2 kg roll. After leaving it for 24 hours, the adhesive strength was measured in a 180 ° peel test in which the material was peeled off at a speed of 300 mm / min in the 180 degree direction using a tensile tester, and evaluation was performed based on the following evaluation criteria. (Compliant with JISZ0237: 2000)
◯: “Adhesive strength is 10 N or more, which is good.”
X: "Adhesive strength is less than 10N and is not practical."

(2) Holding power The obtained adhesive sheet was prepared to have a width of 25 mm and a length of 150 mm. In accordance with JISZ0237: 2000, the peelable sheet is peeled off from the adhesive sheet, and an adhesive layer is attached to a polished stainless steel plate having a width of 30 mm and a length of 150 mm at the lower end of a stainless plate having a width of 25 mm and a width of 25 mm. After one round trip crimping, a load of 1 kg was applied in an atmosphere of 40 ° C., and the mixture was left for 70,000 seconds to measure the holding force. For the evaluation, the length at which the upper end of the adhesive sheet sticking surface was displaced downward was measured.
Evaluation Criteria ◯: “The displaced length of the adhesive sheet is less than 0.5 mm. Good.”
X: "The displaced length of the adhesive sheet is 0.5 mm or more. It is not practical."

(3) Visible light absorption The transmittance of the obtained adhesive sheet was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation), and it was evaluated whether or not the following conditions were satisfied.
⊚: Light transmittance at a wavelength of 400 to 420 nm is less than 1% over the entire region: Good 〇: Light transmittance at a wavelength of 400 to 420 nm is partially less than 1%, others are 1% or more: Practical range Δ: Wavelength 400 to 420 nm Light transmittance is partly 1% or more and less than 10%, others are 20% or more: Not practical ×: Light transmittance of wavelength 400 to 420 nm is 10% or more over the entire region: Not practical

(4) Transparency The transparency of the obtained adhesive sheet was visually evaluated. The evaluation criteria are as follows.
◯: No turbidity is observed. Good Δ: Some turbidity is observed. Practical range ×: Clearly turbidity is observed. Impractical

(5) Light resistance The obtained adhesive sheet was exposed to light having a wavelength of 300 to 400 nm with an illuminance of 60 W / m ² for 100 hours using a xenon weather meter.
〇: Absorbance reduction rate of maximum absorption wavelength is less than 5% Δ: Absorbance reduction rate of maximum absorption wavelength is 5% or more, less than 20% ×: Absorbance reduction rate of maximum absorption wavelength is 20% or more

As shown in Table 6, the ultraviolet absorbing dye of the present invention has a low transmittance per unit weight in the visible light short wavelength region having a wavelength of 400 to 420 nm. It was found that the transparency of the adhesive sheet was not impaired because the addition of a small amount reached a practical range. In particular, it was found that a small amount of addition reached a practical range as compared with Tinuvin 970 of the comparative example.

<Paint>
(Example 6-1)
A paint was prepared by stirring and mixing with the following composition.
Ultraviolet absorbing dye (A-1) 0.2 parts Polyester (Byron GK250, manufactured by Toyobo Co., Ltd.) 9.0 parts Methyl ethyl ketone 90.0 parts

(Examples 6-2 to 6-7, Comparative Examples 6-1 to 6-2)
As shown in Table 7, the same adjustments as in Example 6-1 were performed to obtain the paints of Examples 6-2 to 6-7 and Comparative Examples 6-1 to 6-2, respectively.

(Making of coated material)
The obtained paint was applied to a glass substrate having a thickness of 1000 μm using a bar coater so as to have a dry film thickness of 6 μm, and dried at 100 ° C. for 2 minutes to form a coating film.
(Evaluation of coated material)
The obtained coated material was evaluated by the following method.

[Visible light absorption]
The transmittance of the obtained coated material was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation), and it was evaluated whether or not the following conditions were satisfied.
⊚: Light transmittance at a wavelength of 400 to 420 nm is less than 1% over the entire region: Good 〇: Light transmittance at a wavelength of 400 to 420 nm is partially less than 1%, others are 1% or more: Practical range Δ: Wavelength 400 to 420 nm Light transmittance is partly 1% or more and less than 10%, others are 20% or more: Not practical ×: Light transmittance of wavelength 400 to 420 nm is 10% or more over the entire region: Not practical

[transparency]
The transparency of the obtained coated material was visually evaluated. The evaluation criteria are as follows.
◯: No turbidity is observed. Good Δ: Some turbidity is observed. Practical range ×: Clearly turbidity is observed. Impractical

[Light resistance]
The obtained coated material was exposed to light having a wavelength of 300 to 400 nm with an illuminance of 60 W / m ² for 100 hours using a xenon weather meter.
〇: Absorbance reduction rate of maximum absorption wavelength is less than 5% Δ: Absorbance reduction rate of maximum absorption wavelength is 5% or more, less than 20% ×: Absorbance reduction rate of maximum absorption wavelength is 20% or more

As shown in Table 7, the ultraviolet absorbing dye of the present invention has a low transmittance per unit weight in the visible light short wavelength region having a wavelength of 400 to 420 nm. It was found that the transparency of the coated product was not impaired because the addition of a small amount reached a practical range. In particular, it was found that a small amount of addition reached a practical range as compared with Tinuvin 970 of the comparative example.

<Photocurable composition>
(Example 7-1)
Each raw material was stirred and mixed with the following composition to prepare a photocurable composition.
UV Absorbing Dye (A-1) 1.0 Part Photopolymerizable Compound (Polyfunctional Acrylate "KAYARADDPHA" manufactured by Nippon Kayaku Co., Ltd.) 18.0 Part Photopolymerization Initiator (IGM ResinBV "Omnirad 184") 1.0 Part Propylene Glycol monomethyl ether 80.0 parts

(Examples 7-2 to 7-11, Comparative Examples 7-1 to 7-2)
As shown in Table 8, the same preparations as in Example 7-1 were prepared, and the photocurable compositions of Examples 7-2 to 7-11 and Comparative Examples 7-1 to 7-2 were obtained, respectively.

(Making of coated material)
The above photocurable composition was applied to a glass substrate having a thickness of 1 mm using a bar coater so as to have a dry film thickness of 6 μm. The obtained coating layer was dried at 100 ° C. for 1 minute, and then cured by irradiating with an ultraviolet ray ^{of 400 mJ / cm 2 with a high-pressure mercury lamp to prepare a coated product.}
(Evaluation of coated material)
The obtained coated material was evaluated by the following method.

[Scratch resistance]
The coated material was set in a Gakushin tester, and was shaken 10 times with a load of 250 g using steel wool. The degree of scratches on the taken-out coated material was judged according to the following five-step visual evaluation. The larger the value, the better the scratch resistance of the cured film.
5: There are no scratches.
4: Slightly scratched.
3: There are scratches, but the base material is not visible.
2: The cured film is partially peeled off due to scratches.
1: The cured film is peeled off and the base material is exposed.

[Pencil hardness]
Based on JIS-K5600, using a pencil hardness tester (Scratching Tester HEIDON-14 manufactured by HEIDON), the hardness of the pencil lead was changed in various ways, and the cured film of the coated product was tested 5 times with a load of 500 g. Did. The hardness of the core when it was not scratched even once or was scratched only once out of 5 times was defined as the pencil hardness of the cured film. The evaluation criteria are as follows.
A: 2H or more.
B: H.
C: Lower than H.

As shown in Table 8, the ultraviolet absorbing dye of the present invention has a low transmittance per unit weight in the visible light short wavelength region having a wavelength of 400 to 420 nm. It was found that the transparency of the coated product was not impaired because the addition of a small amount reached a practical range. In particular, it was found that a small amount of addition reached a practical range as compared with Tinuvin 970 of the comparative example. It was also found that a structure having a photocurable portion gives a superior result in pencil hardness.

This application was filed on December 24, 2019, Japanese Application Japanese Patent Application No. 2019-232191, Japanese Application Japanese Patent Application No. 2020-145817, filed on August 31, 2020, and October 28, 2020. Claim priorities based on Japanese Application Japanese Patent Application No. 2020-180124 and Japanese Application Japanese Patent Application No. 2020-189607 filed on November 13, 2020, all of which are incorporated herein by reference.

Claims

An ultraviolet absorbing dye (A), which is a triazine compound that absorbs light in an ultraviolet region having a wavelength of less than 400 nm and a visible light short wavelength region having a wavelength of 400 to 420 nm and is bonded to one, two, or three naphthalene rings, and a resin. A resin composition containing.
The resin composition according to claim 1, wherein the resin contains a 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 resin composition according to claim 2, which is a melt-kneaded product of the ultraviolet absorbing dye (A) and the thermoplastic resin (B).
The ultraviolet absorbing dye (A) has any of claims 1 to 3, wherein at least one naphthalene ring is directly bonded to the triazine ring, and at least one of the naphthalene rings directly attached to the triazine ring has a hydroxyl group at the 2-position. The resin composition according to item 1.
The invention according to any one of claims 1 to 4, wherein the ultraviolet absorbing dye (A) is a compound selected from the group consisting of the following general formulas (1), general formulas (2) and general formulas (3). Resin composition.

(In the general formulas (1) to (3), R 1b to R 1g , R 2a to R 2g , and R 3a to R 3g are independently hydrogen atom, hydroxyl group, fluorine atom, chlorine atom, bromine atom, and iodine. It is an 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 2 to 20 carbon atoms, an alcoholic group having 1 to 20 carbon atoms, and an alkenyloxy group having 2 to 20 carbon atoms. It may have a chlorine atom, a bromine atom, an iodine atom, a nitrile group, a nitro group, a carboxyl group, or a sulfo group, and has an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and 1 to 1 carbon atoms. One or more -O-, -CO-, -COO-, -OCO-, -CONH-, or-between carbon atoms of 20 alcoholic groups and alkenyloxy groups having 2 to 20 carbon atoms. It may be connected by NHCO-.
Ar 1 is an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a biphenyl group, and as a substituent, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms. , Aryl group with 6 to 20 carbon atoms, Arcosidel group with 1 to 20 carbon atoms, Alkoxyoxy group with 2 to 20 carbon atoms, Aryloxy group with 6 to 20 carbon atoms, Fluorine atom, Chlorine atom, Bromine atom, Iodine atom , Anitrile group, a nitro group, a carboxyl group, or a sulfo group.
Further, in the general formulas (2) to (3), R 4 , R 5 , and R 6 are independently hydroxyl groups, R 7 or Ar 1 .

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 binding site with the naphthalene ring of the general formulas (1) to (3).

In the general formula (4-2), X 2 and X 3 are independently -CO-, -COO-, -OCO-, -CONH-, or -NHCO-, respectively. R 9 is an arylene group having 6 to 20 carbon atoms. R 10 is R 7 or Ar 1 . However, * in the general formula (4-2) represents the binding site with the naphthalene ring of the general formulas (1) to (3).

In the 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 the general formula (4-3) represents the binding site with the naphthalene ring of the general formulas (1) to (3). )
The resin composition according to any one of claims 1 to 5, wherein the resin composition contains 0.001 to 5% by mass of the ultraviolet absorbing dye (A).
Any one of claims 1 to 6, comprising a liquid masterbatch (F) containing the ultraviolet absorbing dye (A) and a liquid resin (E) having a viscosity at 25 ° C. of 10,000 mPa · s or less. The resin composition according to.
The resin composition according to claim 7, wherein the liquid masterbatch (F) further contains a resin type dispersant (G).
The resin composition according to claim 7 or 8, which contains 50% by mass or more of the liquid resin (E) in 100% by mass of the liquid masterbatch (F).
The resin composition according to any one of claims 7 to 9, wherein the liquid resin (E) has a number average molecular weight of 200 to 2000.
The resin composition according to any one of claims 7 to 10, wherein the liquid resin (E) is at least one selected from the group consisting of a fatty acid polyester resin, a polyalkylene glycol resin, and a polyether ester resin. ..
The resin composition according to any one of claims 7 to 11, wherein the liquid masterbatch (F) is contained in an amount of 0.1 to 5% by mass in 100 parts by mass of the resin composition.
A molded product obtained by molding the resin composition according to any one of claims 1 to 12.