CN114846085B - Resin composition and molded article - Google Patents

Resin composition and molded article Download PDF

Info

Publication number
CN114846085B
CN114846085B CN202080086665.2A CN202080086665A CN114846085B CN 114846085 B CN114846085 B CN 114846085B CN 202080086665 A CN202080086665 A CN 202080086665A CN 114846085 B CN114846085 B CN 114846085B
Authority
CN
China
Prior art keywords
group
resin
general formula
ultraviolet
carbon atoms
Prior art date
Legal status (The legal status 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 status listed.)
Active
Application number
CN202080086665.2A
Other languages
Chinese (zh)
Other versions
CN114846085A (en
Inventor
日水秋生
辰巳僚一
千叶优美香
胡皓
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyocolor Co Ltd
Artience Co Ltd
Original Assignee
Toyo Ink SC Holdings Co Ltd
Toyocolor Co Ltd
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/en
Priority claimed from JP2020189607A external-priority patent/JP2022078729A/en
Application filed by Toyo Ink SC Holdings Co Ltd, Toyocolor Co Ltd filed Critical Toyo Ink SC Holdings Co Ltd
Publication of CN114846085A publication Critical patent/CN114846085A/en
Application granted granted Critical
Publication of CN114846085B publication Critical patent/CN114846085B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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

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

The purpose of the present application is to provide a resin composition which absorbs ultraviolet rays having a wavelength of less than 400nm and also absorbs light in the short wavelength region of visible light having a wavelength of about 400nm to 420nm and which can form a molded article having excellent transparency, and a molded article. The resin composition comprises an ultraviolet-absorbing dye (A) which absorbs light in the ultraviolet region having a wavelength of less than 400nm and in the visible light short wavelength region having a wavelength of 400 to 420nm, and a resin, and is a triazine compound bonded to one, two or three naphthalene rings.

Description

Resin composition and molded article
The present application claims priority based on japanese patent application publication nos. 2019-232191, 2020-145817, 2020-2020 and 2020-11-2020, and 2020-189607, and the disclosure of which is incorporated herein in its entirety.
Technical Field
The present application relates to a pigment-containing resin composition and a molded article.
Background
Heretofore, a resin molded body (hereinafter referred to as a molded body) has been used as a packaging material for a pharmaceutical agent, a cosmetic, or the like. It is known that organic substances in the contents of these packaging materials are generally degraded by the action of ultraviolet rays contained in sunlight or the like.
It is pointed out that: in sunlight, not only ultraviolet rays with a wavelength of less than 400nm but also light with a wavelength of about 400nm to 420nm in a short wavelength region of visible light may cause damage to organic matters or human bodies. Therefore, it is effective to suppress deterioration of the content that the molded article contains an ultraviolet absorber that also absorbs ultraviolet light and light in a short wavelength region of visible light having a wavelength of about 400nm to 420 nm. Further, the property of the ultraviolet absorber is required to be excellent in light resistance without deterioration due to exposure to ultraviolet rays over a long period of time.
Examples of the application of the other molded article include optical applications, such as a polarizing plate protective film used in a liquid crystal display device, an antireflection film, and a surface film for preventing deterioration of a light emitting element of an organic Electroluminescence (EL) display device.
In such optical applications, there is a high-temperature processing process for the composition, and on the other hand, a molded article is required to have a high level of dimensional stability. In particular, since the molding process temperature of a composition containing engineering plastics is as high as, for example, 260 to 340 ℃, the ultraviolet absorber needs heat resistance to withstand high temperatures.
Patent documents 1 to 2 disclose benzotriazole ultraviolet absorbers that absorb light in a short wavelength region of visible light having a wavelength of about 400nm to 420 nm.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2018-177696
Patent document 2: japanese patent laid-open publication No. 2016-514756
Disclosure of Invention
Problems to be solved by the invention
The conventional ultraviolet absorber has a problem that it has low heat resistance and cannot be used for molded articles of thermoplastic resins (e.g., engineering plastics) having a high melting point or a high softening point. Further, the conventional ultraviolet absorber has a low absorption coefficient per unit weight, and the molded article needs to be thickened in order to absorb the visible light in the short wavelength region. On the other hand, there is also a problem that the transparency of the molded body decreases when the amount of the ultraviolet absorber is increased.
The purpose of the present invention is to provide a resin composition which can absorb not only ultraviolet rays having a wavelength of less than 400nm but also light in the short wavelength region of visible light having a wavelength of about 400nm to 420nm and which can form a molded article having excellent transparency.
Technical means for solving the problems
The resin composition of the present invention is a resin composition comprising an ultraviolet-absorbing dye (A) which absorbs light in the ultraviolet region having a wavelength of less than 400nm and in the visible short wavelength region having a wavelength of 400 to 420nm, and a thermoplastic resin (B), and is a triazine compound bonded to one, two or three naphthalene rings.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a resin composition that absorbs not only ultraviolet rays having a wavelength of less than 400nm but also light in a short wavelength region of visible light having a wavelength of about 400nm to 420nm and that can form a molded article having excellent transparency can be provided.
Detailed Description
The resin composition and the molded article according to the present embodiment will be described below.
The term "to" representing the numerical range is defined to include the lower limit value and the upper limit value unless otherwise specified.
[ resin composition ]
The resin composition of the present embodiment contains an ultraviolet-absorbing dye (A) which absorbs light in the ultraviolet region having a wavelength of less than 400nm and in the visible light short wavelength region having a wavelength of 400 to 420nm, and a thermoplastic resin (B), and is a triazine compound bonded to one, two or three naphthalene rings.
Ultraviolet absorbing pigment (A) >, and method for producing the same
In this embodiment, the ultraviolet absorbing dye (a) absorbs light in the short wavelength region of visible light having a wavelength of about 400nm to 420nm in addition to light in the ultraviolet region having a wavelength of less than 400nm by the action of naphthalene ring bonded to triazine ring. The ultraviolet absorbing pigment (a) can be added in a small amount to achieve a desired wavelength absorption as compared with the conventional pigment. Therefore, the transparency of the molded article can be suppressed from being lowered. The ultraviolet absorbing pigment (A) is excellent in heat resistance, and has heat resistance that can withstand melt kneading at 270 ℃ or higher, for example. In the ultraviolet absorbing pigment (a), the naphthalene ring is preferably directly bonded to the triazine ring without a linking group. Further, one to three naphthalene rings directly bonded to the triazine ring are more preferable, and a hydroxyl group is present at the 2-position of at least one naphthalene ring.
The ultraviolet absorbing pigment (a) is preferably a compound selected from the group consisting of the following general formula (1), general formula (2) and general formula (3).
[ chemical 1]
(in the general formulae (1) to (3), R 1b ～R 1g 、R 2a ～R 2g 、R 3a ～R 3g Each independently is a hydrogen atom, a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitrile group, a nitro group, a sulfo group, or R 7 、Ar 1 Or a group represented by the following general formulae (4-1) to (4-3).
R 7 Alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkenyloxy group having 2 to 20 carbon atoms, and may have a hydroxyl group, fluorine atom, chlorine atom, bromine atom, iodine atom, nitrile group, nitro group, carboxyl group, or sulfo group as a substituent, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms between the carbon atoms of the alkenyloxy group having 2 to 20 carbon atoms, one or more-O-; -CO-, -COO-, -OCO-, -CONH-, or-NHCO-.
Ar 1 Aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, biphenyl group, and may have a hydroxyl group, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkenyloxy group having 2 to 20 carbon atoms, 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 a substituent.
In general formulae (2) to (3), R is 4 、R 5 、R 6 Are respectively and independently hydroxy, R 7 Or Ar 1 。
[ chemical 2]
In the general formula (4-1)，X 1 is-CO-, -COO-, -OCO- -CONH-, or-NHCO-. R is R 8 Is hydrogen atom, hydroxy, R 7 Or Ar 1 . Wherein, in the general formula (4-1), the bonding site with naphthalene ring of the general formula (1) to the general formula (3) is represented.
[ chemical 3]
In the general formula (4-2), X 2 、X 3 Are each independently-CO-, -COO-, -OCO-, -CONH-, or-NHCO-. R is R 9 Is arylene group having 6 to 20 carbon atoms. R is R 10 Is R 7 Or Ar 1 . Wherein, in the general formula (4-2), the bonding site with naphthalene ring of the general formula (1) to the general formula (3) is represented.
[ chemical 4]
In the general formula (4-3), X 4 、X 5 Are each independently-CO-, -COO-, -OCO-, -CONH-, or-NHCO-. R is R 11 An alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, which is straight or branched. R is R 12 Is R 7 Or Ar 1 . n is 1 to 20. Wherein, in the general formula (4-3), the bonding site with naphthalene ring of the general formula (1) to the general formula (3) is represented. )
The group represented by the general formula (4-1) is preferably a group represented by the general formula (4).
[ chemical 5]
In the general formula (4), Y is-NH-, or-O-. R is R 13 Is hydrogen atom, hydroxyl group, alkyl group with 1-20 carbon atoms, alkenyl group with 2-20 carbon atoms, aryl group with 6-20 carbon atoms, alkoxy group with 1-20 carbon atoms, alkenyloxy group with 2-20 carbon atoms, aryloxy group with 6-20 carbon atoms, fluorine atom, chlorine atom and bromine as substituent An atom, an iodine atom, a nitrile group, a nitro group, a carboxyl group, or an alkyl group having 1 to 20 carbon atoms of a sulfo group, or an aryl group having 6 to 20 carbon atoms. Wherein the label of formula (4) represents a bonding site to the naphthalene ring of formulas (1) to (3).
The compounds represented by the general formula (1) are, for example, the following compounds.
[ chemical 6]
[ chemical 7]
[ chemical 8]
[ chemical 9]
The compounds represented by the general formula (2) are, for example, the following compounds.
[ chemical 10]
The compounds represented by the general formula (3) are, for example, the following compounds.
[ chemical 11]
As the synthesis method of the triazine compound, a known synthesis method of a compound having a triazine structure can be used for synthesisAnd (3) forming the finished product. For example, a method in which naphthol or a naphthol derivative and cyanuric chloride are subjected to an addition reaction using aluminum trichloride is mentioned. In addition, for example, a method in which methyl 2-hydroxy-1-naphthoate and benzamidine hydrochloride are subjected to condensation cyclization reaction using sodium methoxide may be mentioned. Naphthalene ring or R bonded to triazine ring by single bond 4 、R 5 、R 6 The substituents included may be introduced after formation of the triazine structure or may be introduced prior to formation of the triazine structure.
The content of the ultraviolet absorbing pigment (a) in 100% by mass of the resin composition is preferably 0.001% by mass to 5% by mass, more preferably 0.005% by mass to 1% by mass.
< resin >)
The present resin composition contains a resin. The resin preferably contains a thermoplastic resin, a thermosetting resin, or a photocurable resin in terms of ease of forming a molded body. The present resin composition contains an ultraviolet absorbing pigment (a) having excellent heat resistance, and therefore, for example, even a thermoplastic resin (B) can be preferably used.
The thermoplastic resin (B) may be: polyolefin, polyacrylic acid, polyester resin, polyamide resin, polyacetal resin, polyphenylene sulfide resin, polyether ether ketone resin, cycloolefin resin, polyetherimide resin, polyamideimide resin, polyethersulfone resin, polysulfone resin, polyarylate resin, polyphenylene oxide resin, polycarbonate resin, and the like. The thermoplastic resin (B) may be used singly or in combination of two or more.
Since the present resin composition contains the ultraviolet absorbing pigment (a) having excellent heat resistance, the thermoplastic resin (B) preferably contains a crystalline resin having a melting point of 200 ℃ or higher or an amorphous resin having a glass transition temperature of 120 ℃ or higher. Among these, the crystalline resin preferably has a melting point of 220℃or higher. On the other hand, the melting point is preferably 500℃or lower. The glass transition temperature of the amorphous resin is more preferably 130℃or higher. On the other hand, the glass transition temperature is preferably 300 ℃ or lower. The melting point and the glass transition temperature can be measured by a differential scanning calorimeter, a thermogravimetric differential thermal analysis device, or the like.
Examples of the crystalline resin having a melting point of 200℃or higher include: polyester resins, polyamide resins, polyacetal resins, polyphenylene sulfide resins, polyether ether ketone resins, and the like.
Examples of the amorphous resin having a glass transition temperature of 120℃or higher include: cycloolefin resin, polyetherimide resin, polyamideimide resin, polyethersulfone resin, polysulfone resin, polyarylate resin, polyphenylene oxide resin, polycarbonate resin, and the like.
(polyester resin)
The polyester resin is a crystalline resin having an ester bond in the main chain of the molecule, and examples thereof include: polycondensates synthesized from dicarboxylic acids (including derivatives thereof) and diols (diols or diphenols); polycondensates synthesized from dicarboxylic acids (including derivatives thereof) and cyclic ether compounds; ring-opening polymers of cyclic ether compounds, and the like. The polyester resin may be any of a homopolymer formed of a polymer of a dicarboxylic acid and a diol, a copolymer using various raw materials, and a polymer blend obtained by mixing them. Examples of the derivative of the dicarboxylic acid include an acid anhydride and an ester. The dicarboxylic acid may be either an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid, but is preferably an aromatic dicarboxylic acid in terms of improving heat resistance.
Examples of the aromatic dicarboxylic acid include: terephthalic acid, isophthalic acid, phthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, isophthalic acid, terephthaloyl acid, diphenyldiacetic acid, diphenyl-p, p ' -dicarboxylic acid, diphenyl-4, 4' -diacetic acid, diphenylmethane-p, p ' -dicarboxylic acid, diphenylethane-m, m ' -dicarboxylic acid, diphenyldicarboxylic acid, diphenylbutane-p, p ' -dicarboxylic acid, benzophenone-4, 4' -dicarboxylic acid, naphthalene-1, 4-dicarboxylic acid, naphthalene-1, 5-dicarboxylic acid, naphthalene-2, 6-dicarboxylic acid, naphthalene-2, 7-dicarboxylic acid, p-carboxyphenoxyacetic acid, p-carboxyphenoxybutyl acid, 1, 2-diphenoxypropane-p, p ' -dicarboxylic acid, 1, 5-diphenoxypentane-p, p ' -dicarboxylic acid, 1, 6-diphenoxyhexane-p, p ' -dicarboxylic acid, p- (p-carboxyphenoxy) benzoic acid, 1, 2-bis (2-methoxyphenoxy) -ethane-p, 1, 3-bis (2-methoxyphenoxy) -propane, p-bis (2-methoxyphenoxy) -p, 2-diphenoxy pentane, and the like.
Examples of aliphatic dicarboxylic acids include: oxalic acid, succinic acid, adipic acid, suberic acid (core acid), azelaic acid, sebacic acid, dodecanedicarboxylic acid, undecanedicarboxylic acid, maleic acid, fumaric acid, and the like.
Examples of the diol include: ethylene glycol, trimethylene glycol, butane-1, 3-diol, butane-1, 4-diol, 2-dimethylpropane-1, 4-diol, cis-2-butene-1, 4-diol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, cyclohexanedimethanol, and the like. Among these, ethylene glycol, butane-1, 4-diol, and cyclohexanedimethanol are also preferable.
Examples of dihydric phenols include: hydroquinone, resorcinol, bisphenol a, and the like.
Examples of the cyclic ether compound include ethylene oxide and propylene oxide.
The dicarboxylic acid or diol may be used alone or in combination of two or more.
(Polyamide resin)
The polyamide resin is a crystalline resin, and can be synthesized by, for example, 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. Further, a compound having two or more carboxyl groups may be used as the carboxylic acid component.
For example, a known compound (Am) having two or more amino groups can be used, and examples thereof include: aliphatic polyamines such as ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, etc.; aliphatic polyamines containing alicyclic polyamines such as isophorone diamine and dicyclohexylmethane-4, 4' -diamine; aromatic polyamines such as phenylenediamine and xylylenediamine; diamino alcohols such as 1, 3-diamino-2-propanol, 1, 4-diamino-2-butanol, 1-amino-3- (aminomethyl) -3, 5-trimethylcyclohexane-1-ol, 4- (2-aminoethyl) -4,7, 10-triazadecan-2-ol, and 3- (2-hydroxypropyl) -o-xylene- α, α' -diamine.
Examples of the commercial products of the polyamide resin include 6 nylon (manufactured by Toli Co., ltd.), 66 nylon (manufactured by Toli Co., ltd.), and 610 nylon.
(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 alicyclic structure include: norbornene polymers, monocyclic cyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof. Among these, norbornene polymers are also preferable in terms of excellent moldability and transparency. Examples of norbornene monomers include: bicyclo [2.2.1] hept-2-ene (common name: norbornene), tricyclo [4.3.0.12,5] dec-3, 7-diene (common name: dicyclopentadiene), 7, 8-benzotricyclo [4.3.0.12,5] dec-3-ene (common name: methano-tetrahydrofluorene), tetracyclo [4.4.0.12,5.17,10] dodec-3-ene (common name: tetracyclododecene), and the like.
Examples of the commercially available cycloolefin resin include Topas (manufactured by Bao Litsea plastics) and Apel (manufactured by Mitsui chemical Co., ltd.).
(polyetherimide resin)
The polyetherimide resin is an amorphous resin having a glass transition temperature exceeding 180 ℃, has good transparency, and has high strength, high heat resistance, high elastic modulus, and wide chemical resistance. Therefore, it is widely used for various applications such as automobiles, telecommunications, aerospace, electric/electronic, transportation and health care.
One of the processes for producing the polyetherimide resin is by bisphenol A disodium salt (BPA. Na) 2 ) The polymerization of alkali metal salts of dihydroxy aromatic compounds with bis (halophthalimide) is carried out. 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) for the alkali metal salt of the dihydroxy aromatic compound. Second oneThe method is to prepare bis (halophthalic anhydride) in the presence of monofunctional compounds such as phthalic anhydride which form a capping agent. Phthalic anhydride reacts with a portion of the organic diamine to form a monohalo-bis (phthalimide). The monohalo-bis (phthalimide) functions as a capping agent in the polymerization step by reacting with the benzene oxide end groups in the growing polymer chain.
Examples of the commercially available polyetherimide resin include Wutai Mu (ULTEM) (manufactured by Sade basic industries Co., ltd.).
(polycarbonate resin)
The polycarbonate resin is synthesized by reacting a carbonate precursor such as carbonyl chloride or carbonic acid diester with an aromatic dihydroxy compound. In the case of using a synthesis reaction of phosgene, for example, an interfacial method is preferable. In addition, in the case of using a synthesis reaction of a carbonic acid diester, a transesterification method in which a molten reaction is used is preferable.
Examples of the aromatic dihydroxy compound include: 2, 2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxyphenyl) methane, 1-bis (4-hydroxyphenyl) ethane, 2-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2-bis (4-hydroxy-3-methylphenyl) propane bis (hydroxyaryl) alkanes such as 1, 1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2-bis (4-hydroxy-3-bromophenyl) propane, 2-bis (4-hydroxy-3, 5-dibromophenyl) propane, 2-bis (4-hydroxy-3, 5-dichlorophenyl) propane, and 1, 1-bis (4-hydroxyphenyl) cyclopentane、Bis (hydroxyaryl) cycloalkanes such as 1, 1-bis (4-hydroxyphenyl) cyclohexane, dihydroxydiaryl ethers such as 4,4 '-dihydroxydiphenyl ether and 4,4' -dihydroxy-3, 3 '-dimethyldiphenyl ether, dihydroxydiaryl sulfides such as 4,4' -dihydroxydiphenyl sulfide, 4 '-dihydroxy-3, 3' -dimethyldiphenyl sulfide, dihydroxydiaryl sulfoxides such as 4,4 '-dihydroxydiphenyl sulfoxide and 4,4' -dihydroxy-3, 3 '-dimethyldiphenyl sulfoxide, and dihydroxydiaryl sulfones such as 4,4' -dihydroxydiphenyl sulfone and 4,4 '-dihydroxy-3, 3' -dimethyldiphenyl sulfone. In addition, piperazine, dipiperidinylhydroquinone, resorcinol, 4' -di The hydroxydiphenyl groups are mixed and used.
The carbonate precursor may be exemplified by, for example, [ for example ]: diaryl carbonates such as carbonyl chloride, diphenyl carbonate and xylene carbonate, dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, and the like.
The viscosity average molecular weight of the polycarbonate resin is preferably 15,000 ～ 30,000, more preferably 16,000 ～ 27,000. In the present specification, the viscosity average molecular weight is a value obtained by converting the solution viscosity measured at 25 ℃ using methylene chloride as a solvent.
Examples of commercial products of the polycarbonate resin include: you Pilong (Iuppilon) H-4000 (manufactured by Mitsubishi engineering plastics Co., ltd., viscosity average molecular weight of 16,000), you Pilong (manufactured by Mitsubishi engineering plastics Co., ltd., viscosity average molecular weight of 23,000), you Pilong (manufactured by Mitsubishi engineering plastics Co., ltd., viscosity average molecular weight of 27,000) E-2000, and the like.
When the thermoplastic resin (B) has a moderate Melt Flow Rate (MFR), both fluidity and moldability can be achieved at a high level. The MFR of each resin can be measured according to japanese industrial standard jis (Japanese Industrial Standard) K7210, and is preferably in the following range.
The MFR of the thermoplastic resin (B) varies depending on the type of resin, and is preferably 1g/10min to 200g/10min, more preferably 2g/10min to 150g/10min, and still more preferably 5g/10min to 100g/10min at a temperature (about 200 ℃ C. To 320 ℃ C.) exceeding the melting point or glass transition temperature. Hereinafter, preferable MFR will be described for each resin.
The MFR of the polyester resin is preferably 1g/10min to 200g/10min, more preferably 5g/10min to 150g/10min, still more preferably 10g/10min to 150g/10min at 280℃and 2.16 kg.
The MFR of the polycarbonate resin is preferably 1g/10min to 100g/10min, more preferably 2g/10min to 80g/10min, still more preferably 2g/10min to 50g/10min at 300℃C/1.2 kg.
The MFR of the cycloolefin resin is preferably 1g/10min to 100g/10min, more preferably 2g/10min to 80g/10min, still more preferably 5g/10min to 60g/10min at 260℃C/2.16 kg.
The MFR of the polyamide resin is preferably 1g/10min to 100g/10min, more preferably 2g/10min to 80g/10min, still more preferably 5g/10min to 80g/10min at 235℃C/2.16 kg.
The MFR of the polyetherimide resin is preferably 1g/10min to 100g/10min, more preferably 2g/10min to 80g/10min, still more preferably 3g/10min to 50g/10min at 337 ℃/6.6 kg.
The resin composition may contain an additive in addition to the ultraviolet-absorbing pigment (A) and the thermoplastic resin (B). Examples of additives include: near infrared absorbers, light stabilizers, antioxidants, colorants, waxes, and the like. These additives may be used as compounds known in the use of molded articles.
The near infrared ray absorber is used to impart near infrared ray absorption ability to the molded article. Examples of the near infrared ray absorbing agent include: and compounds such as cyanine compounds, diimmonium compounds, squarylium compounds, and subphthalocyanine compounds. The content of the near infrared ray absorber in 100 mass% of the resin composition is preferably 0.01 mass% to 5 mass%.
Light stabilizers are used to impart ultraviolet resistance to shaped articles. The light stabilizer is preferably, for example, a hindered amine light stabilizer. The content of the light stabilizer in 100 mass% of the resin composition is preferably 0.01 mass% to 5 mass%.
Antioxidants are used to reduce the deterioration of molded articles when they are exposed to natural light or artificial light sources and become hot. The antioxidant is preferably, for example, a monophenol type, a bisphenol type, a high molecular type phenol type, a sulfur type, a phosphoric acid type, or the like. The content of the antioxidant in 100 mass% of the resin composition is preferably 0.01 mass% to 5 mass%.
The wax is used to disperse the ultraviolet absorbing pigment more uniformly in the molded article. The dispersant is preferably, for example, a polyolefin wax, a fatty acid ester wax, a partially saponified fatty acid ester wax, a saponified fatty acid wax, or the like. The wax content is preferably 50 to 250 parts by mass per 100 parts by mass of the ultraviolet absorbing pigment (a).
< production of resin composition >
Examples of the method for producing the present resin composition include a method of melt-kneading the ultraviolet absorbing pigment (a) and the thermoplastic resin (B). The resin composition after melt-kneading is preferably cooled.
The melt kneading temperature may be appropriately adjusted depending on the type of the thermoplastic resin (B) used. When a crystalline resin having a melting point of 200 ℃ or more or an amorphous resin having a glass transition temperature of 120 ℃ or more is used as the thermoplastic resin (B), the melt kneading temperature is preferably 270 ℃ or more, more preferably 300 ℃ or more. In particular, a resin such as engineering plastic having high heat resistance is preferably processed at high temperature because of low fluidity. The upper limit of the melt kneading temperature is not limited as long as the components are not decomposed or evaporated, and is preferably 500℃or less, more preferably 450℃or less.
Examples of the melt kneading apparatus include: a single-screw kneading extruder, a twin-screw kneading extruder, a tandem twin-screw kneading extruder, and the like.
The resin composition is preferably prepared as a so-called master batch. When a master batch is produced and then melt-kneaded with a diluent resin (thermoplastic resin (B)) to produce a molded article, the ultraviolet-absorbing pigment (a) is easily dispersed uniformly in the molded article, and aggregation of the ultraviolet-absorbing pigment (a) can be suppressed, as compared with a molded article produced without the master batch. This improves the transparency of the molded article. The master batch is preferably formed into pellets by using a pelletizer after the melt-kneading.
In the case of producing a master batch, the content of the ultraviolet absorbing pigment (a) is preferably 0.01 to 20 mass%, more preferably 0.05 to 2 mass%, based on 100 mass% of the resin composition.
< liquid masterbatch (F) >)
More preferably, the resin composition is produced by preparing a liquid master batch (F) containing the ultraviolet absorbing pigment (a) and the liquid resin (E), and then melt-kneading the master batch with the diluent resin (thermoplastic resin (B)).
(liquid resin (E))
The liquid resin (E) functions as a dispersion medium for dispersing the ultraviolet-absorbing pigment (a).
The liquid resin (E) has a viscosity of 10,000 mPas or less at 25 ℃. The viscosity is more preferably 10 to 5,000 mPas, and still more preferably 100 to 3,000 mPas. When within the range, the ultraviolet absorbing pigment (a) can be easily dispersed in the liquid master batch. The viscosity in the present specification is in accordance with JIS K7117-1:1999 and measured at 25 ℃ using a type B viscometer.
The content of the liquid resin (E) in 100 mass% of the liquid master batch (F) is preferably 50 mass% or more, more preferably 60 mass% to 95 mass%, and still more preferably 70 mass% to 90 mass%. In this range, for example, the melt viscosity can be suppressed during melt kneading, and thus the ultraviolet-absorbing pigment (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, particularly preferably 1000 to 1500. When Mn is 200 or more, both formability and transparency are easily attained. Further, when Mn is 2000 or less, dispersibility and antistatic properties are improved.
Examples of the liquid resin (E) include: epoxy resins such as epoxidized soybean oil and epoxidized flax oil, fatty acid polyester resins, polyalkylene glycol resins, polyether ester resins, and the like are preferable in terms of high heat resistance and excellent antistatic properties when the thermoplastic resin (B) requires a high molding temperature of polyethylene terephthalate (polyethylene terephthalate, PET), polycarbonate, or the like.
The fatty acid polyester resin is a resin obtained by reacting an aliphatic polycarboxylic acid with a polyhydric alcohol.
The aliphatic polycarboxylic acid is an aliphatic carboxylic acid having two or more carboxyl groups. Examples of the aliphatic polycarboxylic acid include: aliphatic polycarboxylic acids such as succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, tricarballylic acid, 1,3, 6-hexanetricarboxylic acid, and 1,3, 5-hexanetricarboxylic acid.
The polyol is an alcohol having two or more hydroxyl groups. Examples of the polyol include: and polyalkylene glycols such as aliphatic diols including ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 2-methyl-1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 2-dimethyl-1, 3-propanediol, 2-diethyl-1, 3-propanediol, 2-n-butyl-2-ethyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 2, 4-trimethyl-1, 3-pentanediol, 2-ethyl-1, 3-hexanediol, 2-methyl-1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 12-octadecanediol, and diethylene glycol and dipropylene glycol.
The aliphatic polycarboxylic acid and the polyhydric alcohol may be used singly or in combination.
The solidification point of the fatty acid polyester resin is preferably-5℃or lower, more preferably-50℃to-10 ℃.
Examples of commercial products of the fatty acid polyester resin include: ai Dike Session (Adeka sizer) PN-170 (manufactured by Ai Dike (ADEKA) company, a viscosity of 800 mPa.s at 25℃with a solidifying point of-15℃with adipic acid polyester resin), ai Dike Session (Adeka sizer) P-200 (manufactured by Ai Dike (ADEKA) company, a viscosity of 2,600 mPa.s at 25℃with a solidifying point of-20℃with adipic acid polyester resin), ai Dike Session (manufactured by Adeka sizer) PN-250 (manufactured by Ai Dike (ADEKA) company, a viscosity of 4,500 mPa.s at 25℃with a solidifying point of-20℃with adipic acid polyester resin), and the like.
The polyether resin is a resin having a repeating unit of an alkylene oxide group. The carbon number of the alkylene oxide group is preferably 1 to 6. The polyether resin preferably has a viscosity of 10,000 mPas or less at 25 ℃. The viscosity is suitable for use in a liquid masterbatch. The alkylene oxide group preferably has 2 to 4 carbon atoms. This improves the compatibility and suppresses the water absorption.
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, polytetramethylene glycol and polytetramethylene glycol having 4 carbon atoms in the repeating unit, and the like.
The polyether ester resin is an ester compound of an aliphatic polycarboxylic acid resin and an alkylene glycol resin.
Examples of commercial products of polyetherester resins include: ai Dike Sehelter (Adeka sizer) RS-107 (manufactured by Adeka corporation, adeka, 25 ℃ C. Viscosity 20 mPa.s, freezing point-47 ℃ C., adipic acid ether ester resin), ai Dike Sehelter (Adeka sizer) RS-700 (manufactured by Ai Dike (ADeka), 25 ℃ C., viscosity 30 mPa.s, freezing point-53 ℃ C., polyether ester resin), and the like.
The solidification point of the liquid resin (E) is preferably-5℃or lower, more preferably-50℃to-10 ℃.
The resin composition is produced by producing a liquid master batch (F) and then melt-kneading the master batch with a diluent resin (thermoplastic resin (B)), and a molded article produced using the resin composition has better transparency than a molded article produced from a conventional solid master batch.
Since the liquid masterbatch (F) contains the liquid resin (E) and is in a liquid state, it has high fluidity in melt kneading with the thermoplastic resin (B), and can disperse the ultraviolet absorbing pigment (a) very uniformly. In particular, resins of engineering plastics having high heat resistance have a limit in fluidity even at a melt kneading temperature. Therefore, it is difficult to uniformly disperse the pigment by aggregation, and it is difficult to improve transparency. Therefore, in the case of the thermoplastic resin (B) which is a crystalline resin having a melting point of 200 ℃ or more or an amorphous resin having a glass transition temperature of 120 ℃ or more, the liquid master batch (F) is effective for improving transparency. In particular, the present invention is effective in applications requiring high transparency, such as optical filters.
The content of the ultraviolet absorbing pigment (a) in the liquid master batch (F) is preferably 1 to 30 mass%, more preferably 2 to 20 mass%, in 100 mass% of the liquid master batch.
(resin-type dispersant (G))
The liquid master batch (F) preferably contains a resin-type dispersant (G). Thus, the ultraviolet absorbing pigment (a) is dispersed more uniformly in the liquid master batch, and the obtained molded article has higher transparency. In addition, the storage stability of the liquid master batch is improved by containing the resin-type dispersing agent (G).
The resin type dispersant (G) is a compound containing an adsorption site having a property of adsorbing the ultraviolet absorbing pigment and a relaxation site having compatibility with components other than the ultraviolet absorbing pigment.
Examples of the resin-type dispersant (G) include: such as polyurethane, polyacrylate, and other polycarboxylic acid esters, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylic acid esters, or modified products of these, amide or salt thereof formed by the reaction of poly (lower alkylene imine) with polyester having free carboxyl groups, and other oily dispersants, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, polyvinyl pyrrolidone, and other water-soluble resins or water-soluble polymer compounds, polyester systems, modified polyacrylate systems, ethylene oxide/propylene oxide addition compounds, phosphate systems, and the like.
The resin type dispersant (G) may be used singly or in combination of two or more.
Among the above resin-type dispersants, a polymer dispersant having a basic functional group is preferable because the viscosity of the dispersion is reduced by a small amount of the resin-type dispersant. Further, a graft copolymer containing a nitrogen atom, an acrylic block copolymer containing a nitrogen atom and a urethane polymer dispersant having a tertiary amino group, a quaternary ammonium salt group, a functional group containing a nitrogen-containing heterocycle, or the like in a side chain, and the like are preferable.
The amount of the resin-type dispersant (G) to be used is preferably about 5 to 200% by mass, and more preferably about 10 to 100% by mass, in view of film-forming property, relative to the ultraviolet-absorbing pigment (a).
Examples of commercially available resin-type dispersants include: disepbik (Disepbyk) -101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, and BYK-Chemie Japan (BYK Japan) 2155 or Anbody Tara-U (Anti-Terra-U), 203, 204, or Pick (BYK) -P104, P104S, 220S, 6919, or Lycra (Lactimon), lycra (Lactimon) -WS, BYkumen, etc., sonupase (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 and the like, and alfuka (EFKA) -46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, and the like, and Fine PB flavor element chemicals (Ajinomoto) of PB (aji) company, aji 111, 824, 822, 824, and the like.
In the case where the resin dispersant (G) is dissolved in an organic solvent, it is preferable to add the liquid resin (E), decompress and heat the mixture, and distill off the solvent.
Method for producing liquid masterbatch (F)
The liquid master batch (F) can be prepared by mixing and dispersing the ultraviolet absorbing pigment (a) and the liquid resin (E). In addition, a resin type dispersant (G) may be used in combination in the dispersion. For example, a dispersing device such as a kneader, a twin roll mill, a three roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, a ring bead mill, or an attritor can be used for the dispersion.
[ molded article ]
The molded article of the present embodiment is obtained by molding a resin composition. The molded article can be produced by directly molding the resin composition. In addition, in the case of preparing the resin composition into a master batch, a molded body can be produced by melt-kneading together with a diluent resin (thermoplastic resin (B)) and then molding. The mass ratio of the master batch (X) to the diluent resin (Y) is preferably X/y=1/5 to 1/500. When the amount is within the above range, the molded article can easily obtain good optical characteristics.
When the liquid masterbatch (F) is used as the masterbatch, the liquid masterbatch (F) is more preferably contained in an amount of 0.1 to 5 mass% based on 100 mass% of the resin composition.
Use of shaped bodies
The molded article can be used for, for example, food packaging materials, medical product packaging materials, displays, glass intermediate films, and lens applications.
The food packaging material or the pharmaceutical product packaging material is preferably a thermoplastic resin such as a polyester resin or a cycloolefin resin. The flexibility and visibility of these molded articles are improved, and deterioration of the content can be suppressed.
The molded article used for displays, glass intermediate films, and lens applications is preferably a film containing a resin having a property transparent to a desired wavelength. The resin constituting such a molded article includes: polyetherimide resins, polyethersulfone resins, polyethylene terephthalate resins, polyimide resins, polysulfone resins, polyarylate resins, polyamide resins, polycarbonate resins, olefin polymer resins having an alicyclic structure (alicyclic olefin polymer resins), cellulose ester resins, and the like.
In display applications, the molded article is used in, for example, optical films used for televisions, personal computers, smart phones, and the like. The laminate using the molded article comprising the present resin composition can suppress adverse effects on the eyes by absorbing light in the short wavelength region of ultraviolet rays or visible light contained in the backlight of a display. In addition, the laminate can suppress degradation of the display element of the display by absorbing light in a short wavelength region of ultraviolet rays or visible light contained in sunlight.
In the application of glass interlayer, the present molded article is used for, for example, laminated glass used for automobiles, buildings, and the like. The laminated glass using the molded article comprising the present resin composition can suppress adverse effects on eyes or human bodies by absorbing light in a short wavelength region of ultraviolet rays or visible light contained in sunlight.
In the field of lens applications, the molded article is used for lenses and the like used for spectacles, optical sensors and the like, for example. The lens using the molded article comprising the present resin composition can suppress adverse effects on eyes or the human body by absorbing light in a short wavelength region of ultraviolet rays or visible light contained in sunlight, for example, in spectacle applications, and can improve the sensitivity of a sensor by blocking light of an unnecessary wavelength which may become noise in optical sensor applications.
The molded article can be widely used for applications such as medical agents, cosmetics, food containers, packaging materials, sundries, fiber products, medical product containers, various industrial coating materials, automobile parts, home appliances, building materials for houses, and cosmetics (cosmetics). Further, the material can be widely used for display materials, sensor materials, optical control materials, and the like.
Examples
The present invention will be described in more detail below. The present invention is not limited to the examples. The "parts by mass" is referred to as "parts" and the "%" is referred to as "%".
Method for producing ultraviolet absorbing pigment (A)
[ ultraviolet-absorbing pigment (A-1) ]
A300 mL Erlenmeyer flask was charged with 170 parts of chlorobenzene, 43.4mmol of cyanuric chloride, 65.1mmol of aluminum chloride, stirred and suspended. Next, while cooling with ice water, 151.8mmol of 2-naphthol was added in small amounts. Then, the mixture was stirred overnight while gradually returning to room temperature. On the other hand, the reaction solution was added dropwise in small amounts successively by charging 38.1 parts of water, 10.0 parts of 35% hydrochloric acid and 45.0 parts of methanol into a 500mL beaker. Further, 45.0 parts of methanol was added to the Erlenmeyer flask in portions, and the flask was rinsed and added to a 500mL beaker. The precipitate was isolated by filtration and spray washed with water/methanol=75 parts/75 parts of mixed solvent. The wet cake obtained was put back into 150 parts of water, reslurried at room temperature for 30 minutes, and separated by filtration. Then, spray cleaning was performed using 150 parts of water. The obtained wet cake was dried at 80℃overnight to obtain an ultraviolet absorbing pigment (A-1).
Nuclear magnetic resonance (nuclear magnetic resonance, NMR) measurement was performed on the ultraviolet-absorbing pigment (A-1), and as a result, a result supporting the structure was obtained. The measurement conditions are as follows.
< measurement Condition >
The device comprises: bruce Azos (BRUKER AVANCE) 400
Resonant frequency: 400MHz (1H-NMR)
A solvent: dimethyl sulfoxide-d 8
Tetramethylsilane was used as an internal standard for 1H-NMR, the chemical shift value was represented by delta value (ppm), and the coupling constant was represented by Hertz (Hertz). S is abbreviated as single, d is abbreviated as double, and m is abbreviated as multiple. The content of the obtained NMR spectrum is 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 other ultraviolet-absorbing pigments were also identified by NMR in the same manner as described above, but the data were omitted.
[ ultraviolet-absorbing pigment (A-2) ]
The ultraviolet absorbing pigment (A-2) was obtained by the same method as that for the production of the ultraviolet absorbing pigment (A-1), except that 1, 3-dihydroxynaphthalene was added instead of 2-naphthol.
[ ultraviolet-absorbing pigment (A-3) ]
The ultraviolet absorbing pigment (A-3) was obtained by the same method as that for the production of the ultraviolet absorbing pigment (A-1), except that 6-bromo-2-naphthol was added instead of 2-naphthol.
[ ultraviolet-absorbing pigment (A-4) ]
A200 mL Erlenmeyer flask was charged with 100 parts of N-methyl-2-pyrrolidone, 20.0mmol of ultraviolet absorbing pigment (A-1), and 40.0mmol of potassium carbonate, and the mixture was heated to 90℃with stirring. Next, 40.0mmol of 1-iodohexane was charged, and stirred at 90℃for 4 hours. On the other hand, 500 parts of water was charged into a 1L beaker, and the reaction solution before the previous reaction was gradually added dropwise in small amounts. The precipitate was separated by filtration and spray-washed with 500 parts of water. The wet cake obtained was put back into 500 parts of water, reslurried at room temperature for 30 minutes, and separated by filtration. Then, spray cleaning was performed using 500 parts of water. The obtained wet cake was dried at 80℃overnight to obtain an ultraviolet absorbing pigment (A-4).
[ ultraviolet-absorbing pigment (A-5) ]
A200 mL Erlenmeyer flask was charged with 100 parts of N-methyl-2-pyrrolidone, 20.0mmol of ultraviolet absorbing pigment (A-2), and 60.0mmol of potassium carbonate, and the mixture was heated to 90℃with stirring. Next, 60.0mmol of 1-iodobutane was charged and stirred at 90℃for 4 hours. On the other hand, 500 parts of water was charged into a 1L beaker, and the reaction solution before the previous reaction was gradually added dropwise in small amounts. The precipitate was separated by filtration and spray-washed with 500 parts of water. The wet cake obtained was put back into 500 parts of water, reslurried at room temperature for 30 minutes, and separated by filtration. Then, spray cleaning was performed using 500 parts of water. The obtained wet cake was dried at 80℃overnight to obtain an ultraviolet absorbing pigment (A-5).
[ ultraviolet-absorbing pigment (A-6) ]
The ultraviolet absorbing pigment (A-6) was obtained by the same method as that for the production of the ultraviolet absorbing pigment (A-1), except that 6-hydroxy-2-naphthol was added instead of 2-naphthol.
[ ultraviolet-absorbing pigment (A-7) ]
The ultraviolet absorbing pigment (A-7) was obtained by the same method as the method for producing the ultraviolet absorbing pigment (A-1), except that 6-hydroxy-2-naphthoic acid was added instead of 2-naphthol.
[ ultraviolet-absorbing pigment (A-8) ]
The ultraviolet absorbing pigment (A-8) was obtained in the same manner as in the production of the ultraviolet absorbing pigment (A-1), except that methyl 6-hydroxy-2-naphthoate was added instead of 2-naphthol.
[ ultraviolet-absorbing pigment (A-9) ]
The ultraviolet absorbing pigment (A-9) was obtained by the same method as that for the production of the ultraviolet absorbing pigment (A-1), except that 2-naphthol-6-sodium sulfonate hydrate was added instead of 2-naphthol.
[ ultraviolet-absorbing pigment (A-10) ]
The ultraviolet absorbing pigment (A-10) was obtained by the same method as the method for producing the ultraviolet absorbing pigment (A-1), except that 3-hydroxy-2-naphthoic acid was added instead of 2-naphthol.
[ ultraviolet-absorbing pigment (A-11) ]
The ultraviolet absorbing pigment (A-11) was obtained by the same method as the method for producing the ultraviolet absorbing pigment (A-1), 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 pigment (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-dihydroxynaphthyl) -1,3, 5-triazine was obtained.
[ ultraviolet-absorbing pigment (A-12) ]
A200 mL Erlenmeyer flask was charged with 100 parts of N-methyl-2-pyrrolidone, 20.0mmol of 2,4, 6-tris (2, 7-dihydroxynaphthyl) -1,3, 5-triazine, and 60.0mmol of triethylamine, and 60.0mmol 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 into a 1L beaker, and the reaction solution before the previous reaction was gradually added dropwise in small amounts. The precipitate was separated by filtration and spray-washed with 500 parts of water. The wet cake obtained was put back into 500 parts of water, reslurried at room temperature for 30 minutes, and separated by filtration. Then, spray cleaning was performed using 500 parts of water. The obtained wet cake was dried at 80℃overnight to obtain an ultraviolet absorbing pigment (A-12).
[ ultraviolet-absorbing pigment (A-13) ]
The ultraviolet absorbing pigment (A-13) was obtained by the same method as that used for the production of the ultraviolet absorbing pigment (A-12) except that trimethylacetyl chloride was added instead of acetyl chloride.
[ ultraviolet-absorbing pigment (A-14) ]
The ultraviolet absorbing pigment (A-14) was obtained by the same method as that for the production of the ultraviolet absorbing pigment (A-1), except that 5-acetyl-2-naphthol was added instead of 2-naphthol.
[ ultraviolet-absorbing pigment (A-15) ]
The ultraviolet-absorbing pigment (A-15) was obtained in the same manner as in the production of the ultraviolet-absorbing pigment (A-1), except that 3-hydroxy-2-naphthoylaniline was added instead of 2-naphthol.
[ ultraviolet-absorbing pigment (A-16) ]
The ultraviolet absorbing pigment (A-16) was obtained by the same method as that for the production of the ultraviolet absorbing pigment (A-1), except that 3-hydroxy-2' -methoxy-2-naphthoylaniline was added instead of 2-naphthol.
[ ultraviolet-absorbing pigment (A-17) ]
The ultraviolet-absorbing pigment (A-17) was obtained by the same method as that for the production of the ultraviolet-absorbing pigment (A-1), except that 5 '-chloro-3-hydroxy-2' -methyl-2-naphthoylaniline was added instead of 2-naphthol.
[ ultraviolet-absorbing pigment (A-18) ]
The ultraviolet-absorbing pigment (A-18) was obtained in the same manner as in the production of the ultraviolet-absorbing pigment (A-1), except that 5 '-chloro-3-hydroxy-2' -methoxy-2-naphthoylaniline was added instead of 2-naphthol.
[ ultraviolet-absorbing pigment (A-19) ]
The ultraviolet absorbing pigment (A-19) was obtained by the same method as that for the production of the ultraviolet absorbing pigment (A-1), except that 3-hydroxy-3' -nitro-2-naphthoylaniline was added instead of 2-naphthol.
[ ultraviolet-absorbing pigment (A-20) ]
A200 mL Erlenmeyer flask was charged with 100 parts of N-methyl-2-pyrrolidone, 20.0mmol of ultraviolet absorbing pigment (A-1) and 60.0mmol of triethylamine, and 40.0mmol of acryloyl chloride was charged while stirring, and the mixture was stirred at room temperature for 4 hours. On the other hand, 500 parts of water was charged into a 1L beaker, and the reaction solution before the previous reaction was gradually added dropwise in small amounts. The precipitate was separated by filtration and spray-washed with 500 parts of water. The wet cake obtained was put back into 500 parts of water, reslurried at room temperature for 30 minutes, and separated by filtration. Then, spray cleaning was performed using 500 parts of water. The obtained wet cake was dried at 80℃overnight to obtain an ultraviolet absorbing pigment (A-20).
[ ultraviolet-absorbing pigment (A-21) ]
A200 mL Erlenmeyer flask was charged with 100 parts of N-methyl-2-pyrrolidone and 20.0mmol of 2-methacryloxyethyl succinic acid (Laitter (Light Ester) HO-MS (N), manufactured by Kyowa chemical Co., ltd.) and stirred while being cooled in an ice bath. 20mmol of thionyl chloride was added dropwise thereto, and the mixture was stirred for 2 hours while cooling in an ice bath. Then, 20.0mmol of the ultraviolet absorbing pigment (A-1) was charged, and stirred at room temperature for 4 hours. On the other hand, 500 parts of water was charged into a 1L beaker, and the reaction solution before the previous reaction was gradually added dropwise in small amounts. The precipitate was separated by filtration and spray-washed with 500 parts of water. The wet cake obtained was put back into 500 parts of water, reslurried at room temperature for 30 minutes, and separated by filtration. Then, spray cleaning was performed using 500 parts of water. The obtained wet cake was dried at 80℃overnight to obtain ultraviolet absorbing pigment (A-21).
[ ultraviolet-absorbing pigment (A-22) ]
A200 mL Erlenmeyer flask was charged with 100 parts of N-methyl-2-pyrrolidone and 40.0mmol of 2-methacryloxyethyl succinic acid (Laitter (Light Ester) HO-MS (N), manufactured by Kyowa chemical Co., ltd.) and stirred while being cooled in an ice bath. 40mmol of thionyl chloride was added dropwise and stirred for 2 hours while cooling in an ice bath. Then, 20.0mmol of the ultraviolet absorbing pigment (A-1) was charged, and stirred at room temperature for 4 hours. On the other hand, 500 parts of water was charged into a 1L beaker, and the reaction solution before the previous reaction was gradually added dropwise in small amounts. The precipitate was separated by filtration and spray-washed with 500 parts of water. The wet cake obtained was put back into 500 parts of water, reslurried at room temperature for 30 minutes, and separated by filtration. Then, spray cleaning was performed using 500 parts of water. The obtained wet cake was dried at 80℃overnight to obtain ultraviolet absorbing pigment (A-22).
[ ultraviolet-absorbing pigment (A-23) ]
Ultraviolet Light absorbing pigment (A-23) was obtained by the same method as that used for the production of ultraviolet Light absorbing pigment (A-22), except that omega-carboxyl-polycaprolactone (n.about.2) monoacrylate (Luo Nisi (Aronix) M-5300, manufactured by Tokyo Co., ltd.) was added instead of 2-methacryloyloxyethyl succinic acid (Lat Ester (Light Ester) HO-MS (N), manufactured by Kyowa chemical Co., ltd.).
[ ultraviolet-absorbing pigment (A-24) ]
Ultraviolet absorbing pigment (A-24) was obtained by the same method as that used for the production of ultraviolet absorbing pigment (A-22), except that monohydroxyethyl phthalate (Aronix) M-5400, manufactured by east Asia Synthesis Co., ltd.) was added in place of 2-methacryloyloxyethyl succinate (Lat Ester (Light Ester) HO-MS (N), manufactured by Kyowa chemical Co., ltd.).
[ ultraviolet-absorbing pigment (A-25) ]
A300 mL Erlenmeyer flask was charged with 170 parts of chlorobenzene, 43.4mmol of 2-chloro-4, 6-di (naphthalen-1-yl) -1,3, 5-triazine, 65.1mmol of aluminum chloride, stirred and suspended. Next, 65.1mmol of 2-naphthol was added in small portions while cooling with ice water. Then, the mixture was stirred overnight while gradually returning to room temperature. On the other hand, the reaction solution was added dropwise in small amounts successively by charging 38.1 parts of water, 10.0 parts of 35% hydrochloric acid and 45.0 parts of methanol into a 500mL beaker. Further, 45.0 parts of methanol was added to the Erlenmeyer flask in portions, and the flask was rinsed and added to a 500mL beaker. The precipitate was isolated by filtration and spray washed with water/methanol=75 parts/75 parts of mixed solvent. The wet cake obtained was put back into 150 parts of water, reslurried at room temperature for 30 minutes, and separated by filtration. Then, spray cleaning was performed using 150 parts of water. The obtained wet cake was dried at 80℃overnight to obtain an ultraviolet absorbing pigment (A-25).
[ ultraviolet-absorbing pigment (A-26) ]
A300 mL Erlenmeyer flask was charged with 170 parts of chlorobenzene, 43.4mmol of 2, 4-dichloro-6-phenyl-1, 3, 5-triazine, 65.1mmol of aluminum chloride, and stirred and suspended. Next, while cooling with ice water, 108.5mmol of 2-naphthol was added in small portions. Then, the mixture was stirred overnight while gradually returning to room temperature. On the other hand, the reaction solution was added dropwise in small amounts successively by charging 38.1 parts of water, 10.0 parts of 35% hydrochloric acid and 45.0 parts of methanol into a 500mL beaker. Further, 45.0 parts of methanol was added to the Erlenmeyer flask in portions, and the flask was rinsed and added to a 500mL beaker. The precipitate was isolated by filtration and spray washed with water/methanol=75 parts/75 parts of mixed solvent. The wet cake obtained was put back into 150 parts of water, reslurried at room temperature for 30 minutes, and separated by filtration. Then, spray cleaning was performed using 150 parts of water. The obtained wet cake was dried at 80℃overnight to obtain ultraviolet absorbing pigment (A-26).
[ ultraviolet-absorbing pigment (A-27) ]
The ultraviolet light-absorbing pigment (A-27) was obtained by the same method as that for the production of the ultraviolet light-absorbing pigment (A-26), except that 2- (4-biphenyl) -4, 6-dichloro-1, 3, 5-triazine was added instead of 2, 4-dichloro-6-phenyl-1, 3, 5-triazine.
[ production of ultraviolet-absorbing pigment (A-28) 1 (A-28-1) ]
The ultraviolet light-absorbing pigment (A-28) was obtained by the same method as that for the production of the ultraviolet light-absorbing pigment (A-25), except that 2-chloro-4, 6-diphenyl-1, 3, 5-triazine was added instead of 2-chloro-4, 6-bis (naphthalen-1-yl) -1,3, 5-triazine.
[ production of ultraviolet-absorbing pigment (A-28) 2 (A-28-2) ]
A500 mL Erlenmeyer flask was charged with 420mmol of methyl 2-hydroxy-1-naphthoate and heated to 90℃with stirring. Next, 128mmol of benzamidine hydrochloride, 26 parts of a 30% solution of sodium methoxide were charged and stirred at 90℃for 22 hours. Then, 200 parts of methanol was charged, cooled to room temperature and filtered. The wet cake obtained was put back into 150 parts of methanol, reslurried at room temperature for 30 minutes, and separated by filtration. Then, spray cleaning was performed using 150 parts of methanol. The obtained wet cake was dried at 80℃overnight to obtain an ultraviolet absorbing pigment (A-28). The ultraviolet absorbing pigment (A-28) thus produced 2 was synthesized into the same compound (A-28) by a different synthetic route from that of the above-mentioned production 1.
[ ultraviolet-absorbing pigment (A-29) ]
The ultraviolet absorbing pigment (A-29) was obtained in the same manner as in the production of the ultraviolet absorbing pigment (A-28-2), except that p-methylbenzamidine hydrochloride was added instead of benzamidine hydrochloride.
[ ultraviolet-absorbing pigment (A-30) ]
The ultraviolet absorbing pigment (A-30) was obtained in the same manner as in the production of the ultraviolet absorbing pigment (A-28-2), except that p-butoxybenzamidine hydrochloride was added instead of benzamidine hydrochloride.
[ ultraviolet-absorbing pigment (A-31) ]
The ultraviolet light-absorbing pigment (A-31) was obtained by the same method as the method for producing the ultraviolet light-absorbing pigment (A-25), except that 2-chloro-4, 6-dimethoxy-1, 3, 5-triazine was added instead of 2-chloro-4, 6-di (naphthalen-1-yl) -1,3, 5-triazine.
[ ultraviolet-absorbing pigment (A-32) ]
The ultraviolet light-absorbing pigment (A-32) was obtained by the same method as that for the production of the ultraviolet light-absorbing pigment (A-25), except that 2, 4-bis [4- (t-butyl) phenyl ] -6-chloro-1, 3, 5-triazine was added in place of 2-chloro-4, 6-bis (naphthalen-1-yl) -1,3, 5-triazine.
[ ultraviolet-absorbing pigment (A-33) ]
Ultraviolet light-absorbing pigment (A-33) was obtained by the same method as that for the production of ultraviolet light-absorbing pigment (A-25), except that 2- ([ 1,1' -biphenyl ] -4-yl) -4-chloro-6-phenyl-1, 3, 5-triazine was added instead of 2-chloro-4, 6-di (naphthalen-1-yl) -1,3, 5-triazine.
[ absorbance measurement ]
(test example 1 to 35, comparative test example 1 to comparative test example 6)
The results of measuring the ultraviolet-visible absorption spectra of the ultraviolet-absorbing pigments (A-1) to (A-33) and the ultraviolet-absorbing agents of the following comparative pigments (AA-1) to (AA-3) are shown in Table 1. The comparative pigment used the following ultraviolet absorber. The ultraviolet absorbers were evaluated for visible light absorbability and the like, with a transmittance of less than 10% being confirmed in all the wavelength regions having a wavelength of 320nm or more and less than 400 nm.
(AA-1) Di-fir (Tinuvin) 970 (manufactured by BASF JAPAN, japan) benzotriazole-based ultraviolet absorber
(AA-2) Di-fir (Tinuvin) 460 (manufactured by BASF JAPAN Co., ltd., triazine ultraviolet absorbent)
(AA-3) LA-F70 (Ai Dike (manufactured by ADEKA) Co., ltd., triazine-based ultraviolet 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 ultraviolet absorbers each having no naphthalene ring.
The method for preparing a solution for measuring absorbance and the measurement conditions are as follows.
Solution preparation method
1 part of ultraviolet absorbing pigment (A-1) and 1000 parts of tetrahydrofuran were mixed and completely dissolved. Then, 1 part of the previous solution and 99 parts of tetrahydrofuran were uniformly mixed to prepare a solution having a concentration of 10 ppm.
The ultraviolet absorbers of the ultraviolet absorbing pigments (A-2) to (A-33) and the comparative pigments (AA-1) to (AA-3) were also prepared so as to have the concentrations shown in Table 1.
< measurement Condition >
The device comprises: ultraviolet visible near infrared spectrophotometer U-3500 (Hitachi manufacturing company)
Measurement wavelength: 260nm to 700nm
A solvent: tetrahydrofuran (THF)
Concentration: is described in Table 1
The evaluation criteria for the ultraviolet to visible absorption spectra are as follows.
And (3) the following materials: the absorbance at a wavelength of 400nm to 420nm is 0.3 or more over the entire region: good quality
O: the absorbance at a wavelength of 400nm to 420nm is partially 0.3 or more, and the other absorbance is less than 0.3: practical field
Delta: the absorbance at a wavelength of 400nm to 420nm is partially 0.1 or more and less than 0.3, and the other is less than 0.1: cannot be practically used
X: the absorbance at a wavelength of 400nm to 420nm is less than 0.1 in the whole region: cannot be practically used
TABLE 1
As shown in table 1, it is clear that the ultraviolet absorbing pigment (a) used in the resin composition of the present invention has a high absorbance per unit weight in the visible light short wavelength region having a wavelength of 400nm to 420nm, as compared with the ultraviolet Absorbing Agent (AA) used in the conventional resin composition.
< thermoplastic resin (B) >)
(B-1) Polyester (Polyester) MA-2101M (Polyester resin, you Niji available from Unitika Co., ltd., crystalline resin, melting point 264 ℃ C., MFR 45g/10min (280 ℃ C./2.16 kg))
(B-2) You Pilong (Iupplon) S-3000 (polycarbonate resin, manufactured by Mitsubishi engineering plastics Co., ltd.), amorphous resin, glass transition temperature 145 ℃ C., MFR 15g/10min (300 ℃ C./1.2 kg)
(B-3) Topas 6013M-07 (cycloolefin resin, manufactured by Polyplastic Co., ltd., amorphous resin, glass transition temperature 142 ℃ C., MFR 13g/10min (260 ℃ C./2.16 kg))
(B-4) xylonite (Apel) (cycloolefin resin, amorphous resin manufactured by Sanjing chemical Co., ltd.), glass transition temperature 135℃and MFR 11g/10min or more (260 ℃ C./2.16 kg)
(B-5) Amiran CM3001-N (Polyamide resin, manufactured by Toli Co., ltd., crystalline resin, melting point 265 ℃ C., MFR 7g/10min or more (235 ℃/2.16 kg))
(B-6) Wutaimu (ULTEM) (polyetherimide resin, manufactured by Saint Foundation Industrial Co., ltd., amorphous resin, glass transition temperature 217 ℃ C., MFR 8g/10min or more; 337 ℃ C./6.6 kg)
< liquid resin (E) >)
(E-1): you Niao celluloid (Unior) D-1200 (polyalkylene glycol resin, polypropylene glycol resin, number average molecular weight 1200, viscosity 200 mPa.s manufactured by Nitro oil Co., ltd.)
(E-2): PEG-400 (polyalkylene glycol resin, polypropylene glycol resin, number average molecular weight 400, viscosity 90 mPa.s, manufactured by Sanyo chemical industry Co., ltd.)
(E-3): you Niao celluloid (Unior) D-400 (polyalkylene glycol resin, polypropylene glycol resin, number average molecular weight 400, viscosity 100 mPa.s manufactured by Nitro oil Co., ltd.)
(E-4): ai Dike Seze (Adeka sizer) RS-107 (manufactured by Adeka corporation, addiso, ether ester resin, adipic acid Ether ester resin, number average molecular weight 430, viscosity 20 mPa.s)
(E-5): ai Dike Seze (Adeka sizer) RS-700 (Ai Dike (ADEKA) company, ether ester resin, number average molecular weight 550, viscosity 30 mPa. Multidot.s)
(E-6): ai Dike Seze (Adeka sizer) PN-250 (Ai Dike (ADEKA) manufactured by the company, fatty acid polyester resin, adipic acid polyester resin, number average molecular weight 2100, viscosity 4,500 mPa.s)
(E-7): ai Dike Seze (Adeka sizer) PN-350 (Ai Dike (ADEKA) company, fatty acid polyester resin, adipic acid polyester resin, number average molecular weight 4500, viscosity 10,000 mPa.s)
Resin dispersant (G) >)
(production of resin-type dispersant solution (G-1))
To the resin type dispersant solution (G-1) of the non-volatile component/liquid resin (E-4) =1/1 of the pith (BYK) -LPN6919 manufactured by the japan pith chemical company having a non-volatile component of 60%, the liquid resin (E-4) equivalent to the pith (BYK) -LPN6919 was added, heated to 100 ℃ and distilled off under reduced pressure to remove the solvent.
[ Synthesis of ethylenically unsaturated monomer (b-5) ]
A reaction vessel including a stirrer and a thermometer was charged with 60 parts of ethyl methacrylate, 29 parts of 3- (dimethylamino) propylamine, and 120 parts of Tetrahydrofuran (THF), and stirred at room temperature for 5 hours. After completion of the reaction was confirmed by Fourier transform infrared spectroscopy (Fourier Transform Infrared, FT-IR), the solvent was distilled off by a rotary evaporator to obtain 73 parts of the following ethylenically unsaturated monomer (b-5) as a pale yellow transparent liquid (yield 82%). The identification of the obtained compound was carried out by 1H-NMR.
[ Synthesis of ethylenically unsaturated monomer (b-9) ]
6.6 parts of the ethylenically unsaturated monomer (b-5) obtained in the synthesis of the ethylenically unsaturated monomer (b-5) and 5 parts of ion-exchanged water were charged into a reaction vessel comprising a stirrer and a thermometer, and after stirring at room temperature, 8 parts of a 35% aqueous hydrochloric acid solution was added dropwise. The completion of the reaction was confirmed by the amine number measurement, and 20 parts of an aqueous solution of ethylenically unsaturated monomer (b-9) was obtained as a pale yellow transparent liquid. The identification of the obtained compound was carried out by 1H-NMR.
[ chemical 12]
(production of resin-type dispersant solution (G-2))
17.7 parts of methyl methacrylate, 53.2 parts of n-butyl methacrylate and 13.2 parts of tetramethyl ethylenediamine are charged into a reaction vessel equipped with a gas introduction pipe, a condenser, a stirring blade and a thermometer, and nitrogen substitution is performed in the system by stirring at 50℃for 1 hour while flowing nitrogen. Next, 2.6 parts of bromoisobutyric acid ethyl ester, 5.6 parts of cuprous chloride, and 100 parts of PGMAc were charged, and the temperature was raised to 110 ℃ under a nitrogen stream to start the polymerization of the first block. After 4 hours of polymerization, the polymerization solution was sampled and measured for nonvolatile components, and it was confirmed that the polymerization conversion was 98% or more in terms of nonvolatile components.
Next, 20 parts of PGMAc, 21.2 parts of an ethylenically unsaturated monomer (b-5) as a second block monomer, and 27 parts (nonvolatile matter 38%) of an aqueous solution of the ethylenically unsaturated monomer (b-9) were charged into the reaction vessel, and the reaction was continued while stirring under a nitrogen atmosphere at 110 ℃. After 2 hours, the polymerization solution was sampled and measured for nonvolatile components, and the conversion of the nonvolatile components was confirmed to be 98% or more in the polymerization conversion of the second block, and the polymerization was stopped by cooling the reaction solution to room temperature.
PGMAc was added to the previously synthesized block copolymer solution so that the nonvolatile content became 40 mass%. Thus, a resin type dispersant solution having an amine value of 50mgKOH/g, a quaternary ammonium salt value of 20mgKOH/g, a weight average molecular weight (Mw) of 9,800 and a nonvolatile content of 40 mass% per unit nonvolatile content was obtained.
Further, a liquid resin (E-4) equivalent to the nonvolatile content of the resin-type dispersant solution was added, and PGMAc and water were distilled off by heating to 100 ℃ and reducing the pressure, thereby obtaining a resin-type dispersant solution (G-2) in which the nonvolatile content of the resin-type dispersant solution/liquid resin (E-4) =1/1.
Example 1-1
< manufacturing of masterbatch >
2 parts of an ultraviolet absorbing pigment (A-1) and 98 parts of a thermoplastic resin (B-1) were fed from the same feed port into a twin-screw extruder (manufactured by Nippon Steel Co., ltd.) having a screw diameter of 30mm, melt-kneaded at 300℃and then cut into pellets by a pelletizer to prepare a master batch (D-1).
Film formation
10 parts of the obtained master batch (D-1) was mixed with 90 parts of the thermoplastic resin (B-1) as a diluent resin, and melt-mixed at a temperature of 300℃using a T-die forming machine (Toyo-type precision machine), thereby forming a film (X-1) having a thickness of 250. Mu.m.
(examples 1-2 to 1-40, comparative examples 1-1 to 1-6)
As in example 1-1, films (X-2) to (X-40) and films (Y-1) to (Y-6) each having a thickness of 250 μm were formed using the materials shown in tables 2-1 to 2-2.
Examples 1 to 41
< manufacturing of liquid masterbatch (F) >)
10 parts of ultraviolet absorbing pigment (A-1) and 90 parts of liquid resin (E-1) were kneaded by a roll to prepare a liquid master batch (F-1).
Film formation
The obtained liquid master batch (F-1) was mixed in an amount of 0.5 part with respect to 99.5 parts of the thermoplastic resin (B-3) as a diluent resin, and the mixture was melt-mixed at a temperature of 300℃by using a T-die forming machine (Toyo-type precision machine), thereby forming a film (X-41) having a thickness of 250. Mu.m.
Examples 1 to 42 to examples 1 to 58
As in examples 1 to 41, films (X-42) to (X-58) having a thickness of 250 μm were formed using the materials described in tables 2-1 to 2-2.
Examples 1 to 59
< manufacturing of liquid masterbatch (F) >)
A liquid master batch (F-19) was prepared by dispersing 10 parts of an ultraviolet absorbing pigment (A-1), 20 parts of a resin type dispersing agent (G-1) and 70 parts of a liquid resin (E-1) by a bead mill.
Film formation
The obtained liquid master batch (F-19) was mixed in an amount of 0.5 part with respect to 99.5 parts of the thermoplastic resin (B-3) as a diluent resin, and the mixture was melt-mixed at a temperature of 300℃by using a T-die molding machine (manufactured by Toyo Seiki Seisaku-Miao Ltd.), to thereby form a film (X-59) having a thickness of 250. Mu.m.
Examples 1 to 60 to examples 1 to 77
As in examples 1 to 59, films (X-60) to (X-77) having a thickness of 250 μm were formed using the materials described in tables 2-1 to 2-2.
[ appearance evaluation of molded article ]
Regarding (X-1) to (X-77) and (Y-1) to (Y-6), it was confirmed that a uniform film was formed.
[ ultraviolet absorbability ]
The transmittance of the obtained film was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by shimadzu corporation), and whether or not the following conditions were satisfied was evaluated.
And (3) the following materials: the light transmittance at wavelengths of 400nm to 420nm is less than 1% in the entire region: good quality
O: a light transmittance at a wavelength of 400nm to 420nm is partially less than 1%, and the other is 1% or more: practical field
Delta: a light transmittance at a wavelength of 400nm to 420nm is partially 1% or more and less than 10%, and the other is 20% or more: cannot be practically used
X: the light transmittance at wavelengths of 400nm to 420nm is 10% or more in the entire region: cannot be practically used
Transparency (transparency)
The transparency of the obtained film was evaluated visually. The evaluation criteria are as follows.
O: no turbidity was visible at all. Good quality
Delta: several clouding was seen. Practical field
X: the turbidity was clearly seen. Cannot be practically used
[ light fastness ]
For the obtained film, a xenon weather resistance tester (xenon weather meter) was used at 60W/m 2 Is exposed to light having a wavelength of 300nm to 400nm for 100 hours.
O: the absorbance decrease rate of the maximum absorption wavelength is less than 5%
Delta: the absorbance reduction rate of the maximum absorption wavelength is 5% or more and less than 20%
X: the absorbance reduction rate of the maximum absorption wavelength is 20% or more
< haze value >)
The haze value of the obtained film was measured by a haze meter, and evaluated based on the following criteria.
Very +: an extremely good value of less than 0.2
And (3) the following materials: more than 0.2 and less than 0.5 are very good
O: 0.5 or more but less than 2 is preferable
Delta: 2 or more and less than 5
X: 5 or more cannot be put into practical use
[ Table 2-1]
[ Table 2-2]
As shown in tables 2-1 to 2-2, the resin molded articles of the present invention have low transmittance per unit weight in the short wavelength region of visible light having a wavelength of 400nm to 420 nm. The film has good transparency because the ultraviolet absorbing pigment is added to a small amount of the resin molded product to achieve a practical field. In particular, since the resin molded article obtained by using the resin composition of comparative example Di-Neurovin 970 is excellent in transparency, it can be used in a practical field by adding a small amount.
Example 2-1
< manufacturing of masterbatch >
2 parts of an ultraviolet absorbing pigment (A-1) and 98 parts of a thermoplastic resin (B-1) were fed from the same feed port into a twin-screw extruder (manufactured by Nippon Steel Co., ltd.) having a screw diameter of 30mm, melt-kneaded at 300℃and then cut into pellets by a pelletizer to prepare a master batch (D-1).
Film formation
10 parts of the obtained master batch (D-1) were mixed with 90 parts of the thermoplastic resin (B-1) as a diluent resin, and the mixture was melt-mixed at a temperature of 300℃using a T-die forming machine (Toyo-type precision machine) to prepare a resin composition. Then, the film (XX-1) was formed to a thickness of 250 μm after leaving it at 300℃for 20 minutes.
(examples 2-2 to 2-40, comparative examples 2-1 to 2-6)
In the same manner as in example 2-1, films (XX-2) to (XX-40) and films (YY-1) to (YY-6) were formed to have a thickness of 250 μm using the materials described in Table 2.
Examples 2 to 41
< manufacturing of liquid masterbatch (F) >)
10 parts of ultraviolet absorbing pigment (A-1) and 90 parts of liquid resin (E-1) were kneaded by a roll to prepare a liquid master batch (F-1).
Film formation
The obtained liquid master batch (F-1) was mixed in an amount of 0.5 part with respect to 99.5 parts of the thermoplastic resin (B-3) as a diluent resin, and the mixture was melt-mixed at a temperature of 300℃by using a T-die forming machine (Toyo-type precision machine) to prepare a resin composition. Then, the mixture was left at 300℃for 20 minutes to form a film (XX-41) having a thickness of 250. Mu.m.
(examples 2-42. About. Examples 2-58)
As in examples 2 to 41, films (XX-42) to (XX-58) were formed with a thickness of 250 μm using the materials described in Table 2.
Examples 2 to 59
< manufacturing of liquid masterbatch (F) >)
A liquid master batch (F-19) was prepared by dispersing 10 parts of an ultraviolet absorbing pigment (A-1), 20 parts of a resin type dispersing agent (G-1) and 70 parts of a liquid resin (E-1) by a bead mill.
Film formation
The obtained liquid master batch (F-19) was mixed in an amount of 0.5 part with respect to 99.5 parts of the thermoplastic resin (B-3) as a diluent resin, and the mixture was melt-mixed at a temperature of 300℃by using a T-die forming machine (Toyo-type precision machine) to prepare a resin composition. Then, the mixture was left at 300℃for 20 minutes to form a film (XX-59) having a thickness of 250. Mu.m.
(examples 2-60. About. Examples 2-77)
As in examples 2 to 59, films (XX-60) to (XX-77) were formed with a thickness of 250 μm using the materials described in Table 2.
[ appearance evaluation of molded article ]
Regarding (XX-1) to (XX-77) and (YY-1) to (YY-6), it was confirmed that a uniform film was formed.
[ ultraviolet absorbability ]
The transmittance of the obtained film was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by shimadzu corporation), and whether or not the following conditions were satisfied was evaluated.
And (3) the following materials: the light transmittance at wavelengths of 400nm to 420nm is less than 1% in the entire region: good quality
O: a light transmittance at a wavelength of 400nm to 420nm is partially less than 1%, and the other is 1% or more: practical field
Delta: a light transmittance at a wavelength of 400nm to 420nm is partially 1% or more and less than 10%, and the other is 20% or more: cannot be practically used
X: the light transmittance at wavelengths of 400nm to 420nm is 10% or more in the entire region: cannot be practically used
[ Heat resistance ]
The obtained films (XX-1) to (XX-77) and (YY-1) to (YY-8) were compared with the films (X-1) to (X-40) and (Y-1) obtained in examples (1-1) to (1-77) and comparative examples (1-1) to (1-8) to evaluate the differences in ultraviolet absorptivity. The evaluation criteria are as follows.
And (3) the following materials: the difference in light transmittance at wavelengths of 400nm to 420nm is less than 1%: good quality
O: the difference in light transmittance at wavelengths of 400nm to 420nm is less than 5%: practical field
Delta: the difference in light transmittance at wavelengths of 400nm to 420nm is less than 10%: cannot be practically used
X: the difference in light transmittance at wavelengths of 400nm to 420nm is 10% or more: cannot be practically used
The raw materials and the blending ratios of examples 2-1 to 2-77 and comparative examples 2-1 to 2-8 are the same as those of examples 1-1 to 1-77 and comparative examples 1-1 to 1-8, respectively, and therefore only the results are shown in Table 3.
TABLE 3
As shown in table 3, the resin molded article of the present invention has a small rate of change in ultraviolet absorptivity due to the residence time during melt mixing at the time of film formation. Therefore, it was confirmed to have good heat resistance.
The thermoplastic resins (number average molecular weight: 30,000 or more) used in examples 3 to 7 below are shown below.
(C-1) polyethylene (Sataiku (santec) LD M2270, MFR=7g/10 min, manufactured by Asahi chemical Co., ltd.)
(C-2) polyethylene (noobtai base (Novatec) UJ790, mfr=50 g/10min, manufactured by japan polyethylene corporation)
(C-3) Polypropylene (nogatabase (Novatec) PP FA3EB, mfr=10.5 g/10min, manufactured by Japan Polypro company)
(C-4) polypropylene (Prime Polypro Li Pulao) J226T, mfr=20 g/10min, manufactured by Prime Polymer company
(H-1) polycarbonate (You Pilong (Iupplon) S3000, MFR=15 g/10min, mitsubishi engineering plastics Co., ltd.)
(H-2) polymethacrylic resin (acrylic peter (Acrypet) MF, mfr=14g/10 min, manufactured by Mitsubishi ra (Mitsubishi Rayon) corporation)
(H-3) polyester (Mitsui pet SA135, manufactured by Mitsui chemical Co., ltd.)
(H-4) cycloolefin resin (Topasi (TOPAS) 5013L-10, manufactured by Mitsui chemical Co., ltd.)
(H-5) polyvinyl butyral resin (Mo Bida cellul B20H, manufactured by Kuraray Co., ltd.)
The liquid resins used in the examples are shown below.
(I-1) You Niao celluloid (Unior) D-400 (polyalkylene glycol resin, polypropylene glycol resin, number average molecular weight 400, viscosity 100 mPa. Multidot.s. Manufactured by Nitro oil Co., ltd.)
(I-2) Ai Dike Seze (Adeka sizer) RS-107 (manufactured by Adeka corporation, addiso, an ether ester resin, an adipic acid ether ester resin, a number average molecular weight of 430, a viscosity of 20 mPa.s)
(I-3) Ai Dike Seze (Adeka sizer) PN-6810 (Ai Dike (ADEKA) company, acetyl tributyl citrate, number average molecular weight 190, viscosity 43 mPa.s)
(I-4) Ai Dike Sez (Adeka sizer) PN-250 (Ai Dike (ADEKA) company, aliphatic polyester resin, adipic acid polyester resin, number average molecular weight 2100, viscosity 4,500 mPa.s)
The plasticizers used in the examples are shown below.
(J-1) triethylene glycol-di-2-ethylhexanoate
(J-2) triethylene glycol-di-n-heptanoate
Resin dispersant (K) >)
(production of resin-type dispersant solution (K-1))
To the pith (BYK) -LPN6919 manufactured by the japan pith chemical company having a nonvolatile content of 60%, a liquid resin (I-2) equivalent to the nonvolatile content of the pith (BYK) -LPN6919 was added, and the solvent was distilled off by heating to 100 ℃ and reducing the pressure, thereby obtaining a resin type dispersant solution (K-1) of the nonvolatile content/liquid resin (I-2) =1/1 of the pith (BYK) -LPN 6919.
(production of resin-type dispersant solution (K-2))
To distrbyk (distrbyk) -2000 manufactured by japan pick chemical company having a nonvolatile content of 40%, a liquid resin (I-2) equivalent to the nonvolatile content of distrbyk (distrbyk) -2000 was added, and the solvent was distilled off by heating to 100 ℃ and reducing the pressure, thereby obtaining a resin type dispersant solution (K-2) of distrbyk (distrbyk) -2000 having a nonvolatile content/liquid resin (I-2) =1/1.
Example 3-1
[ production of masterbatch ]
2 parts of an ultraviolet absorbing pigment (A-1) and 100 parts by mass of a polyolefin (C-1) were fed from the same feed port into a twin-screw extruder (manufactured by Nippon Steel Co., ltd.) having a screw diameter of 30mm, melt-kneaded at 240℃and then cut into pellets by a pelletizer to prepare a master batch.
[ film Forming ]
10 parts by mass of the obtained master batch was mixed with 100 parts by mass of polyolefin (C-1) as a diluent resin. Then, a film having a thickness of 250 μm was obtained by melt-mixing and molding at a temperature of 180℃using a T-die molding machine (manufactured by Toyo Seiki Seisaku-ku-ji Co., ltd.).
(examples 3-2 to 3-38, comparative examples 3-1 to 3-6)
A master batch was produced in the same manner as in example 3-1 except that the material of example 3-1 was changed to the material and the amount of the compound shown in Table 4, and films of examples 3-2 to 3-38 and comparative examples 3-1 to 3-6 were produced, respectively.
[ visible light absorbability ]
The transmittance of the obtained film was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by shimadzu corporation), and whether or not the following conditions were satisfied was evaluated.
And (3) the following materials: the light transmittance at wavelengths of 400nm to 420nm is less than 1% in the entire region: good quality
O: a light transmittance at a wavelength of 400nm to 420nm is partially less than 1%, and the other is 1% or more: practical field
Delta: a light transmittance at a wavelength of 400nm to 420nm is partially 1% or more and less than 10%, and the other is 20% or more: cannot be practically used
X: the light transmittance at wavelengths of 400nm to 420nm is 10% or more in the entire region: cannot be practically used
Transparency (transparency)
The transparency of the obtained film was evaluated visually. The evaluation criteria are as follows.
O: no turbidity was visible at all. Good quality
Delta: several clouding was seen. Practical field
X: the turbidity was clearly seen. Cannot be practically used
[ light fastness ]
For the obtained film, a xenon weather resistance tester was used at 60W/m 2 Is exposed to light having a wavelength of 300nm to 400nm for 100 hours.
O: the absorbance decrease rate of the maximum absorption wavelength is less than 5%
Delta: the absorbance reduction rate of the maximum absorption wavelength is 5% or more and less than 20%
X: the absorbance reduction rate of the maximum absorption wavelength is 20% or more
TABLE 4
As shown in Table 4, the ultraviolet absorbing pigment of the present invention has a low transmittance per unit weight in the short wavelength region of visible light having a wavelength of 400nm to 420 nm. It is found that the addition of a small amount achieves a practical field, and therefore the transparency of the film is not impaired. It is found that the use of a small amount of the above-described pigment is more practical than the use of the pigment of comparative example (Tinuvin) 970.
Example 4-1
(production of master batch)
100 parts of polycarbonate (H-1) and 2 parts of ultraviolet absorbing pigment (A-1) were fed from the same feed port into a twin-screw extruder (manufactured by Nippon Steel Co., ltd.) having a screw diameter of 30mm, melt-kneaded at 280℃and then cut into pellets by a pelletizer to prepare a composition (master batch).
(film Forming)
10 parts of the obtained composition was mixed with 100 parts of polycarbonate (H-1) as a diluent resin, and the mixture was melt-mixed at a temperature of 280℃using a T-die forming machine (Toyo Seisaku machine) to form a film having a thickness of 250. Mu.m.
(examples 4-2 to 4-8, comparative examples 4-1 to 4-6)
A master batch was produced in the same manner as in example 4-1 except that the materials and blending amounts of example 4-1 were changed to those shown in Table 5-1, and films of examples 4-2 to 4-8 and comparative examples 4-1 to 4-6 were produced.
Examples 4 to 9
(production of master batch)
100 parts of a polymethacrylic resin (H-2) and 2 parts of an ultraviolet absorbing pigment (A-1) were fed from the same feed port into a twin-screw extruder (manufactured by Nippon Steel Co., ltd.) having a screw diameter of 30mm, melt-kneaded at 240℃and then cut into pellets by a granulator to prepare a composition (master batch).
(film Forming)
10 parts of the obtained composition was mixed with 100 parts of a polymethacrylic resin (H-2) as a diluent resin, and the mixture was melt-mixed at a temperature of 280℃using a T-die forming machine (Toyo-type precision machine) to form a T-die film having a thickness of 250. Mu.m.
Examples 4 to 10 to examples 4 to 16
A master batch was produced in the same manner as in examples 4 to 9 except that the materials and blending amounts of examples 4 to 9 were changed to those shown in Table 5 to 1, and films of examples 4 to 10 to 4 to 16 were produced.
Examples 4 to 17
(production of master batch)
100 parts of polyester (H-3) and 2 parts of ultraviolet absorbing pigment (A-1) were fed from the same feed port into a twin-screw extruder (manufactured by Nippon Steel Co., ltd.) having a screw diameter of 30mm, melt-kneaded at 280℃and then cut into pellets by a pelletizer to prepare a composition (master batch).
(film Forming)
10 parts of the obtained composition was mixed with 100 parts of polyester (H-3) as a diluent resin, and the mixture was melt-mixed at a temperature of 280℃using a T-die forming machine (Toyo Seisaku machine) to form a film having a thickness of 250. Mu.m.
Examples 4 to 18 to examples 4 to 24
A master batch was produced in the same manner as in examples 4 to 17 except that the materials and blending amounts of examples 4 to 17 were changed to those shown in Table 5-1, and films of examples 4 to 18 to 4 to 24 were produced.
Examples 4 to 25
(production of master batch)
100 parts of cycloolefin resin (H-4) and 2 parts of ultraviolet absorbing pigment (A-1) were fed from the same feed port into a biaxial extruder (manufactured by Japanese Steel Co., ltd.) having a screw diameter of 30mm, melt-kneaded at 240℃and then cut into pellets by a granulator to prepare a composition (master batch).
(film Forming)
10 parts of the obtained composition was mixed with 100 parts of a cycloolefin resin (H-4) as a diluent resin, and the mixture was melt-mixed at a temperature of 280℃using a T-die forming machine (Toyo-type precision machine) to form a T-die film having a thickness of 250. Mu.m.
Examples 4 to 26 to examples 4 to 32
A master batch was produced in the same manner as in examples 4 to 25 except that the materials and blending amounts of examples 4 to 25 were changed to those shown in Table 5-1, and films of examples 4 to 26 to 4 to 32 were produced.
Examples 4 to 33
(production of master batch)
100 parts of a polyvinyl butyral resin (H-5) and 2 parts of an ultraviolet-absorbing pigment (A-1) were fed from the same feed port into a twin-screw extruder (manufactured by Nippon Steel Co., ltd.) having a screw diameter of 30mm, melt-kneaded at 240℃and then cut into pellets by a granulator to prepare a composition (master batch).
(film Forming)
10 parts of the obtained composition were mixed with 100 parts of a polyvinyl butyral resin (H-5) as a diluent resin, and the mixture was melt-mixed by a T-die forming machine (Toyo-type precision machine) at a temperature of 280℃to form a T-die film having a thickness of 250. Mu.m.
Examples 4 to 34 to 4 to 40
A master batch was produced in the same manner as in examples 4 to 33 except that the materials and blending amounts of examples 4 to 33 were changed to those shown in Table 5-1, and films of examples 4 to 34 to 4 to 40 were produced.
Examples 4 to 41
(production of liquid masterbatch)
A liquid master batch was prepared by kneading 10 parts of ultraviolet absorbing pigment (A-1) and 90 parts of liquid resin (I-1) with a roll.
(film Forming)
2 parts of the obtained liquid master batch were mixed with 98 parts of a polycarbonate resin (H-1) as a diluent resin, and the mixture was melt-mixed at a temperature of 280℃using a T-die forming machine (Toyo-yo machine), to form a T-die film having a thickness of 250. Mu.m.
Examples 4 to 42 to examples 4 to 82
In the same manner as in examples 4 to 41, liquid masterbatches were produced using the materials described in Table 5 to 2, and films of examples 4 to 42 to 4 to 82 were produced.
Examples 4 to 83
(production of plasticizer Dispersion)
10 parts of an ultraviolet absorbing pigment (A-1) and 90 parts of a plasticizer (J-1) were bead-dispersed to prepare a plasticizer dispersion.
(film Forming)
2 parts of the obtained plasticizer dispersion was mixed with 98 parts of a polycarbonate resin (H-1) as a diluent resin, and the mixture was melt-mixed at a temperature of 280℃using a T-die forming machine (Toyo-type precision machine) to form a T-die film having a thickness of 250. Mu.m.
(examples 4 to 84. About. Examples 4 to 122)
In the same manner as in examples 4 to 83, using the materials described in tables 5 to 3, plasticizer dispersions were produced, and films of examples 4 to 84 to 4 to 122 were produced, respectively.
[ visible light absorbability ]
The transmittance of the obtained film was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by shimadzu corporation), and whether or not the following conditions were satisfied was evaluated.
And (3) the following materials: the light transmittance at wavelengths of 400nm to 420nm is less than 1% in the entire region: good quality
O: a light transmittance at a wavelength of 400nm to 420nm is partially less than 1%, and the other is 1% or more: practical field
Delta: a light transmittance at a wavelength of 400nm to 420nm is partially 1% or more and less than 10%, and the other is 20% or more: cannot be practically used
X: the light transmittance at wavelengths of 400nm to 420nm is 10% or more in the entire region: cannot be practically used
Transparency (transparency)
The transparency of the obtained film was evaluated visually. The evaluation criteria are as follows.
O: no turbidity was visible at all. Good quality
Delta: several clouding was seen. Practical field
X: the turbidity was clearly seen. Cannot be practically used
[ light fastness ]
For the obtained film, a xenon weather resistance tester was used at 60W/m 2 Is exposed to light having a wavelength of 300nm to 400nm for 100 hours.
O: the absorbance decrease rate of the maximum absorption wavelength is less than 5%
Delta: the absorbance reduction rate of the maximum absorption wavelength is 5% or more and less than 20%
X: the absorbance reduction rate of the maximum absorption wavelength is 20% or more
< haze value >)
The haze value of the obtained film was measured by a haze meter, and evaluated based on the following criteria.
Very +: an extremely good value of less than 0.2
And (3) the following materials: more than 0.2 and less than 0.5 are very good
O: 0.5 or more but less than 2 is preferable
Delta: 2 or more and less than 5
X: 5 or more cannot be put into practical use
[ Table 5-1]
[ Table 5-2]
[ tables 5-3]
As shown in tables 5-1 to 5-3, the ultraviolet absorbing pigment (A) has a low transmittance per unit weight in the short wavelength region of visible light having a wavelength of 400nm to 420 nm. It is found that the addition of a small amount achieves a practical field, and therefore the transparency of the film is not impaired. It is found that the use of a small amount of the above-described pigment is more practical than the use of the pigment of comparative example (Tinuvin) 970.
(production example K-1 of adhesive resin)
Using a reaction apparatus comprising a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube, 96.0 parts of n-butyl acrylate, 4.0 parts of 2-hydroxyethyl acrylate, 50% of the total amount, 0.2 parts of 2,2' -azobisisobutyronitrile as a polymerization initiator, 150 parts of ethyl acetate as a solvent were charged into a reaction vessel under a nitrogen atmosphere, and the remaining 50% of the total amount and a proper amount of ethyl acetate were charged into the dropping vessel. After the start of the reaction in the reaction vessel, the contents of the dropping tube and 0.01 part of ethyl acetate diluted 2,2' -azobisisobutyronitrile were added dropwise under reflux. After the completion of the dropwise addition, the reaction was directly carried out for 5 hours while maintaining the reflux state. After the 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 as an acrylic resin. The adhesive resin of production example K-1 obtained had a weight average molecular weight of 50 ten thousand, a nonvolatile content of 40%, and a viscosity of 3,200 mPas.
(production example K-2 of adhesive resin)
Using a reaction apparatus comprising a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube, 96.0 parts of n-butyl acrylate, 50% of the total amount of 4.0 parts of acrylic acid, 0.2 parts of 2,2' -azobisisobutyronitrile as a polymerization initiator, and 150 parts of ethyl acetate as a solvent were charged into a reaction vessel under a nitrogen atmosphere, and the remaining 50% of the total amount and a proper amount of ethyl acetate were charged into the dropping vessel. After the start of the reaction in the reaction vessel, the contents of the dropping tube and 0.01 part of ethyl acetate diluted 2,2' -azobisisobutyronitrile were added dropwise under reflux. After the completion of the dropwise addition, the reaction was directly carried out for 5 hours while maintaining the reflux state. After the 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 as an acrylic resin. The adhesive resin of production example K-2 obtained had a weight average molecular weight of 60 ten thousand, a nonvolatile content of 40%, and a viscosity of 4,000 mPas.
Example 5-1
As an adhesive resin, 0.2 parts of an ultraviolet absorbing pigment (A-1) was mixed with 100 parts of a nonvolatile component of the adhesive resin of production example K-1, 0.1 parts of KBM-403 (produced by Xinyue chemical industry) as a silane coupling agent, and 0.4 parts of trimethylolpropane adduct of toluene diisocyanate (abbreviated as TDI-TMP (tolylene diisocyanate-trimethylol propane), NCO value=13.2, nonvolatile component=75%) as a curing agent were added, and the mixture was sufficiently stirred to obtain an adhesive. Then, the adhesive was applied to a release film of a polyethylene terephthalate substrate having a thickness of 38 μm so that the thickness thereof became 50 μm after drying, and dried for 2 minutes by a hot air oven at 100 ℃. Then, a 25 μm polyethylene terephthalate film was attached to the adhesive layer side, and aged at room temperature for 7 days in this state, thereby obtaining an adhesive sheet.
(examples 5-2 to 5-7, comparative examples 5-1 to 5-2)
As shown in Table 6, 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 force
The obtained adhesive sheet was prepared in a size of 25mm wide and 150mm long. The adhesive layer exposed by peeling the release film from the adhesive sheet was attached to a glass plate at 23℃under a relative humidity of 50%, and was repeatedly pressed by a 2kg roller. After 24 hours of standing, the adhesion was measured in a 180 ° tear test in which the film was peeled off at a speed of 300mm/min in a 180 ° direction using a tensile tester, and evaluated based on the following evaluation criteria. (according to JIS Z0237:2000)
O: the adhesive force is more than 10N, and the adhesive force is good. "
X: "the adhesion is less than 10N, which is not practical. "
(2) Holding force
The obtained adhesive sheet was prepared in a size of 25mm wide and 150mm long. According to JISZ0237:2000 the releasable sheet was peeled off from the adhesive sheet and polished, and an adhesive layer was attached to a portion of a polished stainless steel plate having a width of 30mm and a longitudinal length of 150mm and a width of 25mm and a transverse length of 25mm, and the sheet was repeatedly pressed and bonded once by a 2kg roller, and then a load of 1kg was applied to the sheet at 40℃for 7 ten thousand seconds, whereby the holding force was measured. For evaluation, the length of the downward offset of the upper end portion of the adhesive sheet attaching surface was measured.
Evaluation criterion
O: "the offset length of the adhesive sheet is less than 0.5mm. Good. "
X: the offset length of the adhesive sheet is 0.5mm or more. And is impractical. "
(3) Visible light absorbency
The transmittance of the obtained adhesive sheet was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by shimadzu corporation), and whether or not the following conditions were satisfied was evaluated.
And (3) the following materials: the light transmittance at wavelengths of 400nm to 420nm is less than 1% in the entire region: good quality
O: a light transmittance at a wavelength of 400nm to 420nm is partially less than 1%, and the other is 1% or more: practical field
Delta: a light transmittance at a wavelength of 400nm to 420nm is partially 1% or more and less than 10%, and the other is 20% or more: cannot be practically used
X: the light transmittance at wavelengths of 400nm to 420nm is 10% or more in the entire region: cannot be practically used
(4) Transparency of
The transparency of the obtained adhesive sheet was evaluated visually. The evaluation criteria are as follows.
O: no turbidity was visible at all. Good quality
Delta: several clouding was seen. Practical field
X: the turbidity was clearly seen. Cannot be practically used
(5) Light resistance
For the obtained adhesive sheet, a xenon weather-proof tester was used at 60W/m 2 Is exposed to light having a wavelength of 300nm to 400nm for 100 hours.
O: the absorbance decrease rate of the maximum absorption wavelength is less than 5%
Delta: the absorbance reduction rate of the maximum absorption wavelength is 5% or more and less than 20%
X: the absorbance reduction rate of the maximum absorption wavelength is 20% or more
TABLE 6
As shown in Table 6, the ultraviolet absorbing pigment of the present invention has a low transmittance per unit weight in the short wavelength region of visible light having a wavelength of 400nm to 420 nm. It is found that the addition of a small amount of the adhesive agent brings about a practical field, and therefore the transparency of the adhesive sheet is not impaired. It is found that the use of a small amount of the above-described pigment is more practical than the use of the pigment of comparative example (Tinuvin) 970.
Coating material
Example 6-1
The following compositions were mixed with stirring to prepare a paint.
0.2 part of ultraviolet absorbing pigment (A-1)
9.0 parts of polyester (manufactured by Bayer process (Vylon) GK 250)
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 paints of examples 6-2 to 6-7 and comparative examples 6-1 to 6-2 were obtained by the same adjustment as in example 6-1.
(preparation of coating)
The obtained paint was applied to a glass substrate having a thickness of 1000 μm using a bar coater so that the thickness of the paint was 6 μm in terms of dry film thickness, and dried at 100℃for 2 minutes to form a coating film.
(evaluation of coating)
The obtained coating was evaluated by the following method.
[ visible light absorbability ]
The transmittance of the obtained coating was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by shimadzu corporation), and whether or not the following conditions were satisfied was evaluated.
And (3) the following materials: the light transmittance at wavelengths of 400nm to 420nm is less than 1% in the entire region: good quality
O: a light transmittance at a wavelength of 400nm to 420nm is partially less than 1%, and the other is 1% or more: practical field
Delta: a light transmittance at a wavelength of 400nm to 420nm is partially 1% or more and less than 10%, and the other is 20% or more: cannot be practically used
X: the light transmittance at wavelengths of 400nm to 420nm is 10% or more in the entire region: cannot be practically used
Transparency (transparency)
The transparency of the obtained coating was evaluated visually. The evaluation criteria are as follows.
O: no turbidity was visible at all. Good quality
Delta: several clouding was seen. Practical field
X: the turbidity was clearly seen. Cannot be practically used
[ light fastness ]
For the obtained coating, a xenon weather resistance tester was used at 60W/m 2 Is exposed to light having a wavelength of 300nm to 400nm for 100 hours.
O: the absorbance decrease rate of the maximum absorption wavelength is less than 5%
Delta: the absorbance reduction rate of the maximum absorption wavelength is 5% or more and less than 20%
X: the absorbance reduction rate of the maximum absorption wavelength is 20% or more
TABLE 7
As shown in Table 7, the ultraviolet absorbing pigment of the present invention has a low transmittance per unit weight in the short wavelength region of visible light having a wavelength of 400nm to 420 nm. It is found that the addition of a small amount of the coating composition brings about a practical field, and therefore the transparency of the coated article is not impaired. It is found that the use of a small amount of the above-described pigment is more practical than the use of the pigment of comparative example (Tinuvin) 970.
Photocurable composition
Example 7-1
The raw materials were stirred and mixed in accordance with the following compositions to prepare photocurable compositions.
1.0 part of ultraviolet absorbing pigment (A-1)
18.0 parts of a photopolymerizable compound (polyfunctional acrylate "Kayarad (Kayarad) DPHA", manufactured by Japanese chemical Co., ltd.)
1.0 part of photopolymerization initiator (IGM resin (IGM ResinBV) manufactured "Omnirad (R) 184")
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, photo-curable compositions of examples 7-2 to 7-11 and comparative examples 7-1 to 7-2 were obtained in the same manner as in example 7-1.
(preparation of coating)
The photocurable composition was applied to a glass substrate having a thickness of 1mm using a bar coater so that the dry film thickness became 6. Mu.m. The obtained coating layer was dried at 100℃for 1 minute, and then irradiated with 400mJ/cm by a high-pressure mercury lamp 2 And hardening the ultraviolet rays of (2) to prepare a coated article.
(evaluation of coating)
The obtained coating was evaluated by the following method.
[ visible light absorbability ]
The transmittance of the obtained coating was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by shimadzu corporation), and whether or not the following conditions were satisfied was evaluated.
And (3) the following materials: the light transmittance at wavelengths of 400nm to 420nm is less than 1% in the entire region: good quality
O: a light transmittance at a wavelength of 400nm to 420nm is partially less than 1%, and the other is 1% or more: practical field
Delta: a light transmittance at a wavelength of 400nm to 420nm is partially 1% or more and less than 10%, and the other is 20% or more: cannot be practically used
X: the light transmittance at wavelengths of 400nm to 420nm is 10% or more in the entire region: cannot be practically used
Transparency (transparency)
The transparency of the obtained coating was evaluated visually. The evaluation criteria are as follows.
O: no turbidity was visible at all. Good quality
Delta: several clouding was seen. Practical field
X: the turbidity was clearly seen. Cannot be practically used
[ scratch resistance ]
The coated article was set on a vibration tester and vibrated 10 times under a load of 250g using steel wool. The coating material taken out was visually evaluated in the following five stages to determine the adhesion of flaws. The larger the number, the better the scratch resistance of the cured film.
5: no flaws at all.
4: a flaw was slightly attached.
3: although a flaw was attached, the substrate was not visible.
2: a flaw was attached, and a part of the cured film was peeled off.
1: the hardened film is peeled off, and the substrate is exposed.
[ Pencil hardness ]
According to JIS-K5600, five tests were conducted under a load of 500g on a cured film of a coated article by changing various hardness of pencil lead using a pencil hardness tester (scratch tester (Scrat ching Tester) New Dong (HEIDON) -14) manufactured by New Dong (HEIDON). The hardness of the core when not damaged at one of the five times or only damaged at one time was taken as the pencil hardness of the cured film. The evaluation criteria are as follows.
A:2H or more.
B：H。
C: lower than H.
[ light fastness ]
For the obtained coating, a xenon weather resistance tester was used at 60W/m 2 Is exposed to light having a wavelength of 300nm to 400nm for 100 hours.
O: the absorbance decrease rate of the maximum absorption wavelength is less than 5%
Delta: the absorbance reduction rate of the maximum absorption wavelength is 5% or more and less than 20%
X: the absorbance reduction rate of the maximum absorption wavelength is 20% or more
TABLE 8
As shown in Table 8, the ultraviolet absorbing pigment of the present invention has a low transmittance per unit weight in the short wavelength region of visible light having a wavelength of 400nm to 420 nm. It is found that the addition of a small amount of the coating composition brings about a practical field, and therefore the transparency of the coated article is not impaired. It is found that the use of a small amount of the above-described pigment is more practical than the use of the pigment of comparative example (Tinuvin) 970. In addition, it is found that the structure having the photo-hardening portion is advantageous in terms of pencil hardness.

Claims (9)

1. A resin composition comprising an ultraviolet-absorbing pigment and a resin, wherein the ultraviolet-absorbing pigment absorbs light in an ultraviolet region having a wavelength of less than 400nm and a visible light short wavelength region having a wavelength of 400nm to 420nm,
the ultraviolet absorbing pigment is a compound selected from the group consisting of the following general formula (1), general formula (2) and general formula (3),
general formula (3)
In the general formulae (1) to (3), R 2a R is R 3a Is hydroxyl; r is R 1b ～R 1g 、R 2b ～R 2g 、R 3b ～R 3g Each independently is a hydrogen atom, a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitrile group, a nitro group, a sulfo group, or R 7 、Ar 1 Or a group represented by the following general formula (4-1) to general formula (4-3);
R 7 alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkenyloxy group having 2 to 20 carbon atoms, and may have a hydroxyl group, fluorine atom, chlorine atom, bromine atom, iodine atom, nitrile group, nitro group, carboxyl group, or sulfo group as a substituent, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms between the carbon atoms of the alkenyloxy group having 2 to 20 carbon atoms, one or more of-O-; -CO-, -COO-, -OCO-, -CONH-, or-NHCO-;
Ar 1 aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, biphenyl group, and may have a hydroxyl group, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkenyloxy group having 2 to 20 carbon atoms, 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 a substituent;
in general formulae (2) to (3), R is 4 、R 5 、R 6 Are respectively and independently hydroxy, R 7 Or Ar 1 ；
General formula (4-1)
＊——X 1 ——R 8
In the general formula (4-1), X 1 is-CO-, -COO-, -OCO- -CONH-, or-NHCO-; r is R 8 Is hydrogen atom, hydroxy, R 7 Or Ar 1 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, in the general formula (4-1), the bonding part of the naphthalene ring in the general formula (1) to the general formula (3) is represented;
general formula (4-2)
＊——X 2 ——R 9 ——X 3 ——R 10
In the general formula (4-2), X 2 、X 3 Are each independently-CO-, -COO-, -OCO-, -CONH-, or-NHCO-; r is R 9 Arylene having 6 to 20 carbon atoms; r is R 10 Is R 7 Or Ar 1 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, in the general formula (4-2), the bonding part with the naphthalene ring of the general formula (1) to the general formula (3);
general formula (4-3)
In the general formula (4-3), X 4 、X 5 Are each independently-CO-, -COO-, -OCO-, -CONH-, or-NHCO-; r is R 11 An alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, which is straight or branched; r is R 12 Is R 7 Or Ar 1 The method comprises the steps of carrying out a first treatment on the surface of the n is 1-20; wherein, in the general formula (4-3), the bonding part with naphthalene ring of the general formula (1) to the general formula (3);
wherein,,
in the general formula (1), R 1b ～R 1g At least one of them is fluorine atom, chlorine atom, bromine atom, iodine atom, nitrile group, nitro group, sulfo group, R 7 、Ar 1 Or a group represented by the general formula (4-1) to the general formula (4-3);
in the general formula (2), R 1b ～R 1g R is R 2b ～R 2g Is a group other than a hydroxyl group; r is R 4 Phenyl, benzyl, which do not include methyl, phenyl having a chlorine atom, and naphthyl having a methyl, methoxy or hydroxy group; and is also provided with
In the general formula (3), R 1b ～R 1g Is a group other than hydroxy or alkoxy, but R 5 R is R 6 Are not phenyl, dimethylphenyl, phenyl with phenoxy or naphthyl with hydroxy,
wherein the ultraviolet absorbing pigment is contained in an amount of 0.001 to 5% by mass in the resin composition.
2. The resin composition of claim 1, wherein the resin comprises a thermoplastic resin.
3. The resin composition according to claim 2, wherein the thermoplastic resin is a crystalline resin having a melting point of 200 ℃ or higher or an amorphous resin having a glass transition temperature of 120 ℃ or higher,
the resin composition is a melt-kneaded product of the ultraviolet absorbing pigment and the thermoplastic resin.
4. The resin composition according to any one of claims 1 to 3, comprising a liquid masterbatch comprising the ultraviolet absorbing pigment and a liquid resin having a viscosity of 10,000 mpa-s or less at 25 ℃.
5. The resin composition according to claim 4, wherein the liquid master batch further contains a resin-type dispersant.
6. The resin composition according to claim 4, wherein the liquid resin is contained in an amount of 50% by mass or more based on 100% by mass of the liquid masterbatch.
7. The resin composition according to claim 4, wherein the number average molecular weight of the liquid resin is 200 to 2000.
8. The resin composition according to claim 4, wherein the liquid resin is one or more selected from the group consisting of aliphatic polyester resins, polyalkylene glycol resins, and polyether ester resins.
9. A molded article obtained by molding the resin composition according to any one of claims 1 to 8.
CN202080086665.2A 2019-12-24 2020-12-22 Resin composition and molded article Active CN114846085B (en)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
JP2019232191 2019-12-24
JP2019-232191 2019-12-24
JP2020-145817 2020-08-31
JP2020145817 2020-08-31
JP2020180124A JP7147827B2 (en) 2019-12-24 2020-10-28 UV absorber, composition, molded article and laminate
JP2020-180124 2020-10-28
JP2020189607A JP2022078729A (en) 2020-11-13 2020-11-13 Resin composition, and molding
JP2020-189607 2020-11-13
PCT/JP2020/047977 WO2021132247A1 (en) 2019-12-24 2020-12-22 Resin composition and molded article

Publications (2)

Publication Number Publication Date
CN114846085A CN114846085A (en) 2022-08-02
CN114846085B true CN114846085B (en) 2023-09-08

Family

ID=76573170

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202080086665.2A Active CN114846085B (en) 2019-12-24 2020-12-22 Resin composition and molded article

Country Status (3)

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

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20240033216A (en) * 2021-07-14 2024-03-12 아티엔스 가부시키가이샤 Ultraviolet absorber and its manufacturing method, composition, molded body, coating film
KR20230017398A (en) * 2021-07-27 2023-02-06 덕산네오룩스 주식회사 Resin composition and display device using the same

Citations (5)

* 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
CN105793362A (en) * 2013-12-18 2016-07-20 横滨橡胶株式会社 Ultraviolet ray-curable resin composition, and laminate
CN106661421A (en) * 2014-11-17 2017-05-10 株式会社艾迪科 Ultraviolet absorber and synthetic resin composition
JP2018131615A (en) * 2017-02-15 2018-08-23 東洋インキＳｃホールディングス株式会社 Coloring resin composition
CN110023405A (en) * 2016-11-28 2019-07-16 三菱工程塑料株式会社 Poly carbonate resin composition

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5874576A (en) * 1995-12-19 1999-02-23 Givaudan-Roure (International) Sa Light screening agents
US6800757B2 (en) * 2001-09-27 2004-10-05 Cytec Technology Corp. Red-shifted triazine ultravioletlight absorbers
EP1463774B1 (en) * 2001-10-18 2013-07-31 Basf Se Naphthyltriazines as stabilizers for organic material
JP5613482B2 (en) * 2009-07-29 2014-10-22 富士フイルム株式会社 Novel triazine derivative, ultraviolet absorber and resin composition
GB201206126D0 (en) * 2012-04-05 2012-05-16 Fujifilm Imaging Colorants Ltd Polymeric dispersants, dispersions, processes for preparing dispersions and the use of polymeric dispersants
KR102214663B1 (en) 2013-04-02 2021-02-10 바스프 에스이 Coated carbon fiber reinforced plastic parts
JP6994748B2 (en) 2017-04-13 2022-01-14 シプロ化成株式会社 Benzotriazole derivative compound

Patent Citations (5)

* 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
CN105793362A (en) * 2013-12-18 2016-07-20 横滨橡胶株式会社 Ultraviolet ray-curable resin composition, and laminate
CN106661421A (en) * 2014-11-17 2017-05-10 株式会社艾迪科 Ultraviolet absorber and synthetic resin composition
CN110023405A (en) * 2016-11-28 2019-07-16 三菱工程塑料株式会社 Poly carbonate resin composition
JP2018131615A (en) * 2017-02-15 2018-08-23 東洋インキＳｃホールディングス株式会社 Coloring resin composition

Also Published As

Publication number Publication date
WO2021132247A1 (en) 2021-07-01
CN114846085A (en) 2022-08-02
KR20220121794A (en) 2022-09-01

Similar Documents

Publication Publication Date Title
CN114846085B (en) Resin composition and molded article
CN1211673C (en) Method for producing polarizing diffraction film
TWI588192B (en) Optical filter, solid-state imaging device and camera module using the optical filter
JP5334369B2 (en) Transparent or translucent dyeable plastic molding compound molding composite
JP4839285B2 (en) Plastic molded product
TWI506080B (en) Thermosetting film forming composition having photo-alignment property
TW200424295A (en) Near-infrared absorptive dye and near-infrared blocking filter
KR20120117791A (en) Optical film, optical film manufacturing method, transparent substrate, image display device, and solar cell
TW201506461A (en) Optical filter and apparatus using the optical filter
WO2007037501A9 (en) Resin composition for forming ultraviolet absorbing layer and laminate comprising ultraviolet absorbing layer
TW201506462A (en) Optical filter and apparatus using the optical filter
TW201704358A (en) Cyanine compound, filter, device using a filter, and resin composition which is applied to CCD CMOS sensors for near-infrared absorption and increasing light resistance
KR20140051074A (en) Optical alignment thermosetting composition, cured layer, color filter, liquid crystal display device, solid state imaging device, patterned retardation plate and optical device
WO2019072202A1 (en) Novel triazine compound, composition thereof, and preparation method therefor
CN113474688B (en) Optical layer and laminate comprising same
JP2013067718A (en) Optical laminated film
JP2002255945A (en) Triazine ring-containing compound, transparent optical molded article, and method for producing them
EP3438157A1 (en) Monomer, polymer, compensation film, optical film, and display device
JP7147827B2 (en) UV absorber, composition, molded article and laminate
JP7164783B1 (en) Ultraviolet absorber and its manufacturing method, composition, molded article, coating film
JP7271690B2 (en) Polycarbonate composition and optical articles formed therefrom
JP2023552125A (en) Resin, its manufacturing method, resin composition, and molded product
JP2022078729A (en) Resin composition, and molding
JP2023012693A (en) Ultraviolet absorber and use thereof
JP2023152199A (en) Ultraviolet absorber, composition, molded article, and coating film

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant