WO2021132247A1 - Composition de résine et article moulé - Google Patents

Composition de résine et article moulé Download PDF

Info

Publication number
WO2021132247A1
WO2021132247A1 PCT/JP2020/047977 JP2020047977W WO2021132247A1 WO 2021132247 A1 WO2021132247 A1 WO 2021132247A1 JP 2020047977 W JP2020047977 W JP 2020047977W WO 2021132247 A1 WO2021132247 A1 WO 2021132247A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
group
carbon atoms
ultraviolet absorbing
resin composition
Prior art date
Application number
PCT/JP2020/047977
Other languages
English (en)
Japanese (ja)
Inventor
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 (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2020180124A external-priority patent/JP7147827B2/ja
Priority claimed from JP2020189607A external-priority patent/JP2022078729A/ja
Application filed by 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 filed Critical 東洋インキＳｃホールディングス株式会社
Priority to KR1020227019241A priority Critical patent/KR20220121794A/ko
Priority to CN202080086665.2A priority patent/CN114846085B/zh
Publication of WO2021132247A1 publication Critical patent/WO2021132247A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2310/00—Masterbatches

Definitions

  • the present invention relates to a resin composition containing a dye and a molded product.
  • molded products resin molded products
  • the organic substances contained in these packaging materials are generally deteriorated by the action of ultraviolet rays contained in sunlight and the like.
  • 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.
  • molded body uses 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.
  • the molded product is required to have a high degree of dimensional stability.
  • 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.
  • 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).
  • 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.
  • 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).
  • 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.
  • 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).
  • 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.
  • 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.
  • R 4 , R 5 , and R 6 are independently hydroxyl groups, R 7 or Ar 1 .
  • X 1 is -CO-, -COO-, -OCO-, -CONH-, or -NHCO-.
  • R 8 is a hydrogen atom, a hydroxyl group, R 7 or Ar 1 .
  • * in the general formula (4-1) represents the binding site with the naphthalene ring of the general formulas (1) to (3).
  • 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 .
  • * in the general formula (4-2) represents the binding site with the naphthalene ring of the general formulas (1) to (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.
  • * 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • thermoplastic resin (B) examples 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.
  • 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.
  • the melting point is preferably 500 ° C. or lower.
  • the glass transition temperature of the amorphous resin is more preferably 130 ° C. or higher.
  • the glass transition temperature is preferably 300 ° C. or lower. Both the melting point and the glass transition temperature can be measured 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.
  • 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-d
  • aliphatic dicarboxylic acid examples 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.
  • the divalent phenol include hydroquinone, resorcinol, bisphenol A and the like.
  • 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.
  • 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.
  • a compound having two or more carboxyl groups can be used.
  • 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- ⁇ and ⁇ '-diamine.
  • Examples of commercially available polyamide resins include 6 nylon (manufactured by Toray Industries, Inc.), 66 nylon (manufactured by Toray Industries, Inc.),
  • 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.
  • 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).
  • Examples of commercially available cycloolefin resins include Topas (manufactured by Polyplastics) and Appel (manufactured by Mitsui Chemicals).
  • 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).
  • BPA ⁇ Na 2 bisphenol A disodium salt
  • halophthalimide 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).
  • 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.
  • a carbonate precursor such as phosgene or carbonic acid diester.
  • phosgene for example, an interfacial method is preferable.
  • 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) cycl
  • 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.
  • 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.
  • thermoplastic resin (B) has an appropriate melt flow rate (MFR)
  • MFR melt flow rate
  • 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.
  • 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).
  • the additive include a near-infrared absorber, a light stabilizer, an antioxidant, a colorant, a wax and the like.
  • compounds known for molding applications can be used.
  • the near-infrared absorber is used to impart near-infrared absorbing ability to the molded product.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • the melt kneading temperature is preferably 270 ° C. or higher, more preferably 300 ° C. or higher. ..
  • 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.
  • melt kneading apparatus examples 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • liquid resin (E) examples 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-oc
  • 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.
  • 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.
  • 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 mP
  • 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.
  • polyether resin examples 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.
  • polytetramethylene glycol and polybutylene glycol having 4 carbon atoms examples 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.
  • 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.
  • 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.
  • the liquid masterbatch (F) preferably contains a resin-type dispersant (G).
  • 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.
  • a polymer dispersant having a basic functional group is preferable because the viscosity of the dispersion decreases with a small amount of addition.
  • 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.
  • 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.
  • the resin type dispersant (G) 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.
  • 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.
  • 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.
  • 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.
  • a molded product can be produced by melt-kneading with a diluted resin (thermoplastic resin (B)) and then molding.
  • liquid masterbatch (F) 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.
  • the molded product can be used, for example, in food packaging materials, pharmaceutical packaging materials, displays, glass interlayer films, and lens applications.
  • thermoplastic resin 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the ultraviolet absorbing dye (A-2) 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).
  • UV absorbing dye (A-3) [Ultraviolet absorbing pigment (A-3)]
  • the ultraviolet absorbing dye (A-3) was obtained by the same method except that 6-bromo-2-naphthol was added instead of 2-naphthol.
  • 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).
  • 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).
  • UV 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.
  • UV 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.
  • UV 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. ..
  • UV absorbing dye (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
  • UV 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.
  • UV 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. ..
  • 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).
  • UV absorbing pigment (A-13) [Ultraviolet absorbing pigment (A-13)]
  • the ultraviolet absorbing dye (A-12) was obtained by the same method except that pivaloyl chloride was added instead of acetyl chloride.
  • UV 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.
  • UV 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.
  • UV 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
  • UV 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.
  • UV 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.
  • UV 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
  • UV absorbing pigment (A-23) [Ultraviolet absorbing pigment (A-23)]
  • ⁇ -carboxypolycaprolactone (n ⁇ 2) monoacrylate instead of 2-methacryloyloxyethyl succinic acid (light ester HO-MS (N), manufactured by Kyoeisha Chemical Co., Ltd.)
  • light ester HO-MS (N) manufactured by Kyoeisha Chemical Co., Ltd.
  • UV 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).
  • UV 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).
  • UV Absorbent Dye (A-28) 1 (A-28-1)
  • 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).
  • an ultraviolet absorbing dye (A-28) of Production 2 synthesized the same compound (A-28) by a synthetic route different from that of Production 1.
  • UV 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.
  • UV 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.
  • UV 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).
  • UV-absorbing pigment (A-32) [Ultraviolet absorbing pigment (A-32)]
  • 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).
  • UV 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).
  • 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) 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.
  • 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 ⁇ : Absorption of wavelength 400 to 420 nm is partly 0.3 or more, others are less than 0.3: Practical range ⁇ : 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
  • 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.
  • 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-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.
  • 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 m
  • 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.
  • 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.
  • 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.
  • Example 1-2 to 1-40 Comparative Examples 1-1 to 1-6
  • the films (X-2) to (X-40) and (Y-1) to (Y-) having a thickness of 250 ⁇ m were used using the materials shown in Tables 2-1 to 2-2. 6) was molded.
  • 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 ⁇ m 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 ⁇ m were formed using the materials shown in Tables 2-1 to 2-2.
  • 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 ⁇ m.
  • Examples 1-60 to 1-77 Similar to Example 1-59, films (X-60) to (X-77) having a thickness of 250 ⁇ m were molded using the materials shown in Tables 2-1 to 2-2.
  • 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
  • ⁇ Light transmittance at a wavelength of 400 to 420 nm is partially less than 1%, others are 1% or more: Practical range
  • ⁇ 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
  • 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.
  • ⁇ Absorbance reduction rate of maximum absorption wavelength is less than 5%
  • ⁇ 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 ⁇ : 0.5 or more and less than 2 Good ⁇ : 2 or more and less than 5 Good ⁇ : 5 or more Not practical
  • 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.
  • Example 2-2 to 2-40 Comparative Examples 2-1 to 2-6
  • films (XX-2) to (XX-40) and (YY-1) to (YY-6) having a thickness of 250 ⁇ m were formed.
  • 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 ⁇ m was formed.
  • Example 2 Similar to Example 2-41, films (XX-42) to (XX-58) having a thickness of 250 ⁇ m were formed using the materials shown in Table 2.
  • 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 ⁇ m was formed.
  • Example 2-60 to 2-77 Similar to Example 2-59, films (XX-60) to (XX-77) having a thickness of 250 ⁇ m were formed using the materials shown in Table 2.
  • 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
  • ⁇ Light transmittance at a wavelength of 400 to 420 nm is partially less than 1%, others are 1% or more: Practical range
  • ⁇ 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
  • ⁇ Difference in light transmittance at wavelength 400 to 420 nm is less than 1%: Good ⁇ : Difference in light transmittance at wavelength 400 to 420 nm is less than 5%: Practical range ⁇ : 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 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.
  • thermoplastic resins used in Examples 3 to 7 below are shown below.
  • 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-1 Polycarbonate (Iupilon S3000
  • 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
  • ⁇ Resin type dispersant (K)> Manufacturing of resin type dispersant solution (K-1)
  • 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.
  • 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.
  • 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.
  • ⁇ Absorbance reduction rate of maximum absorption wavelength is less than 5%
  • ⁇ 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
  • 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 ⁇ m film was molded.
  • Example 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 ⁇ m 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 ⁇ m 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 ⁇ m 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 ⁇ m 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.
  • 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 ⁇ m 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.
  • 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 ⁇ m 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.
  • 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.
  • ⁇ Absorbance reduction rate of maximum absorption wavelength is less than 5%
  • ⁇ 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 ⁇ : 0.5 or more and less than 2 Good ⁇ : 2 or more and less than 5 Good ⁇ : 5 or more Not practical
  • 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.
  • TDI-TMP trimethylolpropan adduct of tolylene diisocyanate
  • this adhesive was applied on a release film of a polyethylene terephthalate base material having a thickness of 38 ⁇ m so as to have a thickness of 50 ⁇ m after drying, and dried in a hot air oven at 100 ° C. for 2 minutes. Then, a 25 ⁇ m 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.
  • Example 5-2 to 5-7 Comparative Examples 5-1 to 5-2
  • 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.
  • 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.”
  • the obtained adhesive sheet was prepared to have a width of 25 mm and a length of 150 mm.
  • 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.
  • 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.
  • 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.”
  • 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.
  • 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
  • Example 7 Comparative Examples 6-1 to 6-2
  • Example 6-1 Comparative Examples 6-1 to 6-2
  • 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.
  • the obtained paint was applied to a glass substrate having a thickness of 1000 ⁇ m using a bar coater so as to have a dry film thickness of 6 ⁇ m, and dried at 100 ° C. for 2 minutes to form a coating film.
  • the obtained coated material was evaluated by the following method.
  • 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.
  • ⁇ Absorbance reduction rate of maximum absorption wavelength is less than 5%
  • ⁇ 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
  • 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
  • Example 7-2 to 7-11 Comparative Examples 7-1 to 7-2
  • Example 7-1 Comparative Examples 7-1 to 7-2
  • 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.
  • 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 ⁇ m.
  • 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.
  • 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.
  • ⁇ Absorbance reduction rate of maximum absorption wavelength is less than 5%
  • ⁇ 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
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Dental Preparations (AREA)

Abstract

L'objet de la présente invention est de fournir une composition de résine qui absorbe non seulement les rayons UV ayant une longueur d'onde inférieure à 400 nm mais également la lumière dans la région de courtes longueurs d'onde de lumière visible ayant une longueur d'onde d'environ 400 à 420 nm et qui permet de mouler des articles moulés ayant une excellente transparence. L'invention concerne également une composition de résine contenant : un pigment (A) absorbant les rayons UV qui est un composé triazine qui absorbe la lumière dans la région UV ayant une longueur d'onde inférieure à 400 nm ainsi que la lumière dans la région de courtes longueurs d'onde de lumière visible ayant une longueur d'onde de 400 à 420 nm, le composé triazine se liant à un, deux ou trois cycles naphtalène ; et une résine.
PCT/JP2020/047977 2019-12-24 2020-12-22 Composition de résine et article moulé WO2021132247A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020227019241A KR20220121794A (ko) 2019-12-24 2020-12-22 수지 조성물, 및 성형체
CN202080086665.2A CN114846085B (zh) 2019-12-24 2020-12-22 树脂组合物、及成形体

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP2019232191 2019-12-24
JP2019-232191 2019-12-24
JP2020145817 2020-08-31
JP2020-145817 2020-08-31
JP2020-180124 2020-10-28
JP2020180124A JP7147827B2 (ja) 2019-12-24 2020-10-28 紫外線吸収剤、組成物、成形体および積層体
JP2020-189607 2020-11-13
JP2020189607A JP2022078729A (ja) 2020-11-13 2020-11-13 樹脂組成物、および成形体

Publications (1)

Publication Number Publication Date
WO2021132247A1 true WO2021132247A1 (fr) 2021-07-01

Family

ID=76573170

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/047977 WO2021132247A1 (fr) 2019-12-24 2020-12-22 Composition de résine et article moulé

Country Status (3)

Country Link
KR (1) KR20220121794A (fr)
CN (1) CN114846085B (fr)
WO (1) WO2021132247A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7164783B1 (ja) * 2021-07-14 2022-11-02 東洋インキＳｃホールディングス株式会社 紫外線吸収剤及びその製造方法、組成物、成形体、塗膜
WO2023008750A1 (fr) * 2021-07-27 2023-02-02 덕산네오룩스 주식회사 Composition de résine et dispositif d'affichage l'utilisant

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1107143A (en) * 1966-02-01 1968-03-20 Ciba Ltd Di-(hydroxynaphthyl)-triazines and processes for their manufacture and use
JPH09176135A (ja) * 1995-12-19 1997-07-08 Givaudan Roure Internatl Sa 遮光剤として有用な化合物
US20030088098A1 (en) * 2001-09-27 2003-05-08 Gupta Ram Baboo Novel red-shifted triazine ultravioletlight absorbers
JP2005506384A (ja) * 2001-10-18 2005-03-03 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド 有機材料の安定剤としてのナフチルトリアジン
JP2011088885A (ja) * 2009-07-29 2011-05-06 Fujifilm Corp 新規なトリアジン誘導体、紫外線吸収剤及び樹脂組成物
JP2015520013A (ja) * 2012-04-05 2015-07-16 フジフィルム イメージング カラーランツ リミテッド ポリマー分散剤、分散液、分散液を調製する工程およびポリマー分散剤の使用
JP2018131615A (ja) * 2017-02-15 2018-08-23 東洋インキＳｃホールディングス株式会社 着色樹脂組成物

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2981579B1 (fr) 2013-04-02 2018-10-17 Basf Se Pièces en plastique renforcées par des fibres de carbone revêtues
JP6026550B2 (ja) * 2013-12-18 2016-11-16 横浜ゴム株式会社 積層体
JP6586346B2 (ja) * 2014-11-17 2019-10-02 株式会社Adeka 紫外線吸収剤及び合成樹脂組成物
CN110023405A (zh) * 2016-11-28 2019-07-16 三菱工程塑料株式会社 聚碳酸酯树脂组合物
JP6994748B2 (ja) 2017-04-13 2022-01-14 シプロ化成株式会社 ベンゾトリアゾール誘導体化合物

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1107143A (en) * 1966-02-01 1968-03-20 Ciba Ltd Di-(hydroxynaphthyl)-triazines and processes for their manufacture and use
JPH09176135A (ja) * 1995-12-19 1997-07-08 Givaudan Roure Internatl Sa 遮光剤として有用な化合物
US20030088098A1 (en) * 2001-09-27 2003-05-08 Gupta Ram Baboo Novel red-shifted triazine ultravioletlight absorbers
JP2005506384A (ja) * 2001-10-18 2005-03-03 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド 有機材料の安定剤としてのナフチルトリアジン
JP2011088885A (ja) * 2009-07-29 2011-05-06 Fujifilm Corp 新規なトリアジン誘導体、紫外線吸収剤及び樹脂組成物
JP2015520013A (ja) * 2012-04-05 2015-07-16 フジフィルム イメージング カラーランツ リミテッド ポリマー分散剤、分散液、分散液を調製する工程およびポリマー分散剤の使用
JP2018131615A (ja) * 2017-02-15 2018-08-23 東洋インキＳｃホールディングス株式会社 着色樹脂組成物

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7164783B1 (ja) * 2021-07-14 2022-11-02 東洋インキＳｃホールディングス株式会社 紫外線吸収剤及びその製造方法、組成物、成形体、塗膜
WO2023286725A1 (fr) * 2021-07-14 2023-01-19 東洋インキＳｃホールディングス株式会社 Absorbeur d'uv et son procédé de fabrication, composition, corps moulé et film de revêtement
WO2023008750A1 (fr) * 2021-07-27 2023-02-02 덕산네오룩스 주식회사 Composition de résine et dispositif d'affichage l'utilisant

Also Published As

Publication number Publication date
KR20220121794A (ko) 2022-09-01
CN114846085A (zh) 2022-08-02
CN114846085B (zh) 2023-09-08

Similar Documents

Publication Publication Date Title
TWI570174B (zh) Near Infrared Cutoff Filter and Device Using Near Infrared Cutoff Filter
JP6245240B2 (ja) ポリカーボネート樹脂組成物、光学フィルム及びポリカーボネート樹脂成形品
CN1211673C (zh) 制造偏振衍射薄膜的方法
JP6108651B2 (ja) ポリカーボネート樹脂組成物、光学フィルム及びポリカーボネート樹脂成形品
JP4759680B2 (ja) 赤外線吸収フィルター
CN100343308C (zh) 脂环式或芳族聚酰胺、聚酰胺膜、使用所述聚酰胺或聚酰胺膜的光学部件以及聚酰胺的共聚物
JP2021088721A (ja) ポリイミド材料、その製造方法およびその製造に用いられるポリイミド前駆体組成物
JP7082872B2 (ja) 高耐熱性ポリカーボネート樹脂及び成形体
TW201321438A (zh) 光學濾器及使用該光學濾器的固體攝影裝置及照相機模組
WO2021132247A1 (fr) Composition de résine et article moulé
TW201506461A (zh) 濾光器及使用前述濾光器的裝置
TW201506462A (zh) 濾光器及使用前述濾光器的裝置
JP2011236336A (ja) 光弾性定数が低いポリカーボネート樹脂および光学成形体
WO2020138050A1 (fr) Composition de résine thermoplastique, et élément optique mettant en œuvre celle-ci
JP7147827B2 (ja) 紫外線吸収剤、組成物、成形体および積層体
JP2022078729A (ja) 樹脂組成物、および成形体
JP7164783B1 (ja) 紫外線吸収剤及びその製造方法、組成物、成形体、塗膜
WO2014168087A1 (fr) Liquide de revêtement, stratifié, instrument optique et équipement électronique
JP2023013321A (ja) 組成物、成形体および塗膜
JP2023152199A (ja) 紫外線吸収剤、組成物、成形体および塗膜
JP6294114B2 (ja) 芳香族−脂肪族ポリカーボネートおよび、それらからなるプラスチックレンズ
JP6857296B1 (ja) 近赤外線吸収顔料および近赤外線吸収性組成物
JP7231466B2 (ja) 透明樹脂積層体
JP2024092315A (ja) 紫外線吸収剤、組成物、成形体および紫外線吸収シート
JP2017137396A (ja) 感圧式接着剤及びそれを用いたフィルム、積層体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20904958

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20904958

Country of ref document: EP

Kind code of ref document: A1