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
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/45—Heterocyclic compounds having sulfur in the ring
• • 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
  • C08J3/203—Solid polymers with solid and/or liquid additives
• • 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
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
  • C08K5/3445—Five-membered rings
• • 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
  • C08K5/3472—Five-membered rings
  • C08K5/3475—Five-membered rings condensed with carbocyclic rings
• • 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
• • 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
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/10—Homopolymers or copolymers of propene
  • C08J2323/12—Polypropene
• • 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
  • C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2333/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2333/06—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
  • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
• • 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
  • C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
• • 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
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • 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
  • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
• • 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
  • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
  • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation

Definitions

• the present invention relates to a kneaded material containing an ultraviolet absorber and a polymer compound.
• the present invention also relates to a method for producing a kneaded product, a molded article and an optical member.
• Patent Documents 1 and 2 describe the use of a benzodithiol compound, which is an ultraviolet absorber, contained in a polymer compound.
• UV absorption performance of UV absorbers may deteriorate over time due to light irradiation.
• an ultraviolet absorber having a maximum absorption wavelength on the longer wavelength side of the ultraviolet region tends to have poor light resistance, and the ultraviolet absorption performance tends to decrease over time.
• an object of the present invention is to provide a kneaded product with excellent resistance to moist heat and light. Another object of the present invention is to provide a method for producing a kneaded product, a molded article and an optical member.
• the present invention provides the following. ⁇ 1> an ultraviolet absorber containing at least one compound selected from compounds represented by formula (1) and compounds represented by formula (2); a polymer compound; A kneaded product containing;
• R 1 and R 2 each independently represent a hydrogen atom, an alkyl group, an aryl group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an ethylenically unsaturated bond-containing group.
• R 3 and R 4 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylamino group, anilino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino represents a group, an alkylthio group, an arylthio group or an ethylenically unsaturated bond-containing group
• R 5 and R 6 each independently represent a hydrogen atom or a substituent
• R 1 and R 3 may combine to form a ring
• R 3 and R 4 may combine to form a ring
• R 2 and R 4 may combine to form a ring
• R 5 and R 6 may combine to form a ring
• at least one of R3 and R4 is a halogen atom, an alkyl group, an aryl group, an alkoxy
• R 13 , R 14 , R 15 and R 16 each independently represent a hydrogen atom or a substituent, R 13 and R 14 may combine to form a ring, R 15 and R 16 may combine to form a ring.
• one of R 3 and R 4 in formula (1) is a hydrogen atom, and the other is a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylamino group, anilino group, or an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, or an ethylenically unsaturated bond-containing group, the kneaded product according to ⁇ 1>.
• the ultraviolet absorber further includes a compound A having a maximum absorption wavelength on the shorter wavelength side than the compound represented by the above formula (1) and the compound represented by the above formula (2).
• ⁇ 6> The kneaded product according to any one of ⁇ 1> to ⁇ 5>, wherein the polymer compound has a glass transition point of ⁇ 80° C.
• the polymer compound includes (meth)acrylic resin, polystyrene resin, polyester resin, polyurethane resin, polythiourethane resin, polyamide resin, polyimide resin, cyclic olefin resin, epoxy resin, polycarbonate resin, vinyl polymer and cellulose.
• Kneading including a step of kneading an ultraviolet absorber containing at least one compound selected from compounds represented by formula (1) and compounds represented by formula (2), and a polymer compound. a method of manufacturing an object;
• R 1 and R 2 each independently represent a hydrogen atom, an alkyl group, an aryl group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an ethylenically unsaturated bond-containing group.
• R 3 and R 4 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylamino group, anilino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino represents a group, an alkylthio group, an arylthio group or an ethylenically unsaturated bond-containing group
• R 5 and R 6 each independently represent a hydrogen atom or a substituent
• R 1 and R 3 may combine to form a ring
• R 3 and R 4 may combine to form a ring
• R 2 and R 4 may combine to form a ring
• R 5 and R 6 may combine to form a ring
• at least one of R3 and R4 is a halogen atom, an alkyl group, an aryl group, an alkoxy
• R 13 , R 14 , R 15 and R 16 each independently represent a hydrogen atom or a substituent, R 13 and R 14 may combine to form a ring, R 15 and R 16 may combine to form a ring.
• R 13 and R 14 may combine to form a ring
• R 15 and R 16 may combine to form a ring.
• the present invention can provide a kneaded product with excellent moist heat resistance and light resistance.
• the present invention can provide a method for producing a kneaded product, a molded article, and an optical member.
• a description that does not describe substitution or unsubstituted includes a group having a substituent as well as a group having no substituent.
• an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
• a numerical range represented by "to” means a range including the numerical values before and after "to" as lower and upper limits.
• total solid content refers to the total amount of components excluding the solvent from all components of the composition.
• (meth)acrylate represents both or either acrylate and methacrylate
• (meth)acryl represents both or either acrylic and methacrylic
• (meth) ) Allyl represents both or either of allyl and methallyl
• (meth)acryloyl represents both or either of acryloyl and methacryloyl.
• process not only means an independent process, but even if it cannot be clearly distinguished from other processes, if the intended action of the process is achieved, the term include.
• the weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as polystyrene equivalent values measured by gel permeation chromatography (GPC).
• the kneaded product of the present invention is a UV absorber containing at least one compound selected from compounds represented by formula (1) and compounds represented by formula (2); a polymer compound; It is characterized by containing
• the compound represented by the formula (1) and the compound represented by the formula (2) have good kneadability with the polymer compound, and the compound represented by the formula (1) and the compound represented by the formula (2)
• the ultraviolet absorber By kneading the ultraviolet absorber containing at least one compound selected from the compounds and the polymer compound, the ultraviolet absorber can be dispersed almost uniformly in the polymer compound, and further, the ultraviolet absorber during kneading. Generation of decomposition products of the agent can also be suppressed. As a result, it is possible to suppress precipitation of the kneaded material and the molded article obtained by using the kneaded material, such as an ultraviolet absorber.
• the kneaded product of the present invention has excellent resistance to moist heat, and by using the kneaded product of the present invention, a molded article having excellent resistance to moist heat can be produced.
• at least one of R 3 and R 4 is a predetermined group other than a hydrogen atom. It is presumed that twisting is likely to occur between 3 and R4 due to effects such as steric repulsion. It is presumed that such twisting reduces the crystallinity of the compound and improves the compatibility between the compound and the polymer compound.
• the compound represented by formula (1) and the compound represented by formula (2) are excellent in light resistance, and the kneaded product of the present invention contains such compounds, so that UV absorption after light irradiation It is possible to suppress the deterioration of the ability and the like. Therefore, the kneaded product of the present invention has excellent light resistance, and by using the kneaded product of the present invention, a molded article having excellent light resistance can be produced.
• the compound represented by the formula (1) and the compound represented by the formula (2) have excellent absorption performance of light with a wavelength of about 400 nm, and the kneaded product of the present invention can absorb light with a wavelength of about 400 nm. It is possible to produce a molded article having excellent shielding properties.
• the compound represented by the formula (1) and the compound represented by the formula (2) are compounds with low fluorescence intensity. It is possible to produce a molded article having excellent ultraviolet absorption ability.
• the molded body When the kneaded material of the present invention is molded into a molded body having a thickness of 0.15 mm, the molded body preferably has a transmittance of 40% or less, more preferably 20% or less, for light having a wavelength of 400 nm. , 15% or less.
• the transmittance of light having a wavelength of 410 nm of the molded article is preferably 60% or less, more preferably 40% or less, and even more preferably 30% or less.
• the transmittance of light having a wavelength of 440 nm of the molded article is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more.
• the fluorescence intensity of the molded body is preferably 10 or less, more preferably 1 or less, and 0.1 More preferably:
• fluorescence intensity is a value measured as follows. That is, the above molded body is irradiated with light of the maximum absorption wavelength of the ultraviolet absorber as excitation light, the emission spectrum is measured, the maximum fluorescence wavelength and the emission intensity at the maximum fluorescence wavelength are obtained, and the emission at the maximum fluorescence wavelength is measured. Let the intensity be the fluorescence intensity. When two or more kinds of ultraviolet absorbers are contained, the maximum absorption wavelength on the longest wavelength side is used as the excitation light.
• the kneaded material of the present invention is preferably pellets.
• pellet means a material obtained by granulating (pelletizing) a kneaded material into a certain shape such as a spherical shape, an ellipsoidal shape, a cylindrical shape, a prismatic shape, or the like.
• the pellet is a master pellet (masterbatch).
• master pellet masterbatch
• a master pellet (masterbatch) is a material in which additives such as high-concentration UV absorbers are dispersed in a polymer compound. Used in combination. In general, precipitation tends to occur as the content of the ultraviolet absorber in the kneaded material increases.
• the kneaded product of the present invention can suppress precipitation of the ultraviolet absorber from the kneaded product even when the content of the ultraviolet absorber is increased. Therefore, the kneaded material of the present invention can be particularly preferably used as a master pellet (masterbatch).
• the kneaded product is obtained by kneading the UV absorber and the polymer compound. That is, the kneaded product in the present specification is obtained by mixing and dispersing an ultraviolet absorber in a polymer compound.
• the kneaded product in this specification is different from a solution in which an ultraviolet absorber and a polymer compound are dissolved or dispersed in a solvent.
• the kneaded material of the present invention contains an ultraviolet absorber.
• the ultraviolet absorber contains at least one compound selected from compounds represented by formula (1) and compounds represented by formula (2).
• the compound represented by Formula (1) and the compound represented by Formula (2) are collectively referred to as a specific compound.
• R 1 and R 2 each independently represent a hydrogen atom, an alkyl group, an aryl group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an ethylenically unsaturated bond-containing group.
• R 3 and R 4 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylamino group, anilino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino represents a group, an alkylthio group, an arylthio group or an ethylenically unsaturated bond-containing group
• R 5 and R 6 each independently represent a hydrogen atom or a substituent
• R 1 and R 3 may combine to form a ring
• R 3 and R 4 may combine to form a ring
• R 2 and R 4 may combine to form a ring
• R 5 and R 6 may combine to form a ring
• at least one of R3 and R4 is a halogen atom, an alkyl group, an aryl group, an alkoxy
• the alkyl groups represented by R 1 and R 2 in formula (1) and the alkyl groups represented by R 11 and R 12 in formula (2) are preferably alkyl groups having 1 to 30 carbon atoms, such as 1 An alkyl group having 1 to 20 carbon atoms is more preferable, an alkyl group having 1 to 15 carbon atoms is more preferable, and an alkyl group having 1 to 10 carbon atoms is particularly preferable.
• the alkyl group may be linear, branched or cyclic, but is preferably a linear or branched alkyl group.
• the alkyl group may have a substituent.
• substituents examples include the groups exemplified for the substituent T described later, preferably an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and more preferably an alkoxycarbonyl group.
• alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, sec-butyl group, tert-butyl group, n-hexyl group, n-octyl group, n-decyl group, eicosyl group, 2-chloroethyl group, 2-cyanoethyl group, benzyl group, 2-ethylbutyl group, 2-ethylhexyl group, 3,5,5-trimethylhexyl group, 2-hexyldecyl group, 2-octyldecyl group, 2-(4, 4-dimethylpentan-2-yl)-5,7,7-trimethyloctyl group, isostearyl group, isopalmityl group, vinyl group, allyl group, prenyl group, geranyl group, oleyl group, propargyl group, cyclohexyl group, cyclopen
• the aryl group represented by R 1 and R 2 in formula (1) and the aryl group represented by R 11 and R 12 in formula (2) are preferably aryl groups having 6 to 30 carbon atoms, such as 6 carbon atoms. ⁇ 10 aryl groups are more preferred.
• the aryl group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later. Specific examples of aryl groups include phenyl, p-tolyl, naphthyl, metachlorophenyl and orthohexadecanoylaminophenyl groups. Preferably, the aryl group is a phenyl group.
• the acyl groups represented by R 1 and R 2 in formula (1) and the acyl groups represented by R 11 and R 12 in formula (2) are preferably acyl groups having 2 to 30 carbon atoms.
• the acyl group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later. Specific examples of acyl groups include acetyl, pivaloyl, 2-ethylhexanoyl, stearoyl, benzoyl, and p-methoxyphenylcarbonyl groups.
• the carbamoyl groups represented by R 1 and R 2 in formula (1) and the carbamoyl groups represented by R 11 and R 12 in formula (2) are preferably carbamoyl groups having 1 to 30 carbon atoms.
• a carbamoyl group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later. Specific examples of the carbamoyl group include N,N-dimethylcarbamoyl group, N,N-diethylcarbamoyl group, morpholinocarbonyl group, N,N-di-n-octylaminocarbonyl group, Nn-octylcarbamoyl group and the like. mentioned.
• the alkoxycarbonyl groups represented by R 1 and R 2 in formula (1) and the alkoxycarbonyl groups represented by R 11 and R 12 in formula (2) include alkoxycarbonyl groups having 2 to 30 carbon atoms.
• the alkoxycarbonyl group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.
• the aryloxycarbonyl group represented by R 1 and R 2 in formula (1) and the aryloxycarbonyl group represented by R 11 and R 12 in formula (2) include aryloxycarbonyl groups having 7 to 30 carbon atoms. .
• the aryloxycarbonyl group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.
• Examples of the ethylenically unsaturated bond-containing groups represented by R 1 and R 2 in formula (1) and the ethylenically unsaturated bond-containing groups represented by R 11 and R 12 in formula (2) include a vinyl group, (meth) Allyl group, (meth)acryloyl group, (meth)acryloyloxy group, (meth)acryloylamino group, vinylphenyl group and groups represented by formula (R100) can be mentioned.
• Rx 1 is represents a hydrogen atom, an alkyl group or an aryl group
• - *1 represents a bond with Y R1
• Y R1 represents a single bond or a divalent linking group
• ZR1 represents a vinyl group, (meth)allyl group, (meth)acryloyl group, (meth)acryloyloxy group, (meth)acryloylamino group or vinylphenyl group.
• the alkyl group represented by Rx 1 is preferably an alkyl group having 1 to 30 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl and the like.
• the aryl group represented by Rx 1 is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. Specific examples include phenyl group, p-tolyl group and naphthyl group.
• Rx 1 is preferably a hydrogen atom.
• the hydrocarbon group includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group, preferably an aliphatic hydrocarbon group.
• the number of carbon atoms in the aliphatic hydrocarbon group is preferably 1-30, more preferably 1-20, even more preferably 1-15.
• the aliphatic hydrocarbon group may be linear, branched or cyclic.
• the cyclic aliphatic hydrocarbon group may be monocyclic or condensed. Moreover, the cyclic aliphatic hydrocarbon group may have a crosslinked structure.
• the number of carbon atoms in the aromatic hydrocarbon group is preferably 6-30, more preferably 6-20, even more preferably 6-10.
• the hydrocarbon group may have a substituent. Substituents include the substituent T described later. For example, a hydroxy group etc. are mentioned as a substituent.
• the divalent linking group represented by Y R1 is preferably a hydrocarbon group or a group in which two or more hydrocarbon groups are linked via a single bond or a divalent linking group.
• Z R1 is preferably a (meth)acryloyloxy group or a vinylphenyl group, more preferably a (meth)acryloyloxy group.
• R 1 and R 2 in formula (1) and R 11 and R 12 in formula (2) are each independently preferably an alkyl group, an acyl group, a carbamoyl group or an ethylenically unsaturated bond-containing group.
• Halogen atoms represented by R 3 and R 4 in formula (1) include fluorine, chlorine and bromine atoms.
• the alkyl group represented by R 3 and R 4 in formula (1) is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. is more preferred, and an alkyl group having 1 or 2 carbon atoms is particularly preferred.
• the alkyl group is preferably a linear or branched alkyl group, more preferably a linear alkyl group.
• the alkyl group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.
• alkyl groups include methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2-cyanoethyl, benzyl, 2-ethylhexyl, vinyl and allyl groups.
• prenyl group, geranyl group, oleyl group, propargyl group, cyclohexyl group, cyclopentyl group, 2-hydroxyethyl group, and 2-hydroxypropyl group preferably methyl group and tert-butyl group, from the viewpoint of ease of synthesis. is more preferably a methyl group.
• the aryl group represented by R 3 and R 4 in formula (1) is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms.
• the aryl group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later. Specific examples of aryl groups include a phenyl group, a paratolyl group, and a naphthyl group.
• the alkoxy group represented by R 3 and R 4 in formula (1) is preferably an alkoxy group having 1 to 30 carbon atoms.
• the alkoxy group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later. Specific examples of alkoxy groups include methoxy and ethoxy groups.
• the aryloxy group represented by R 3 and R 4 in formula (1) is preferably an aryloxy group having 6 to 30 carbon atoms.
• the aryloxy group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later. Specific examples of aryloxy groups include phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy and 2-tetradecanoylaminophenoxy groups.
• the acyloxy group represented by R 3 and R 4 in formula (1) is preferably an acyloxy group having 2 to 30 carbon atoms.
• the acyloxy group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.
• the alkylamino group represented by R 3 and R 4 in formula (1) is preferably an alkylamino group having 1 to 30 carbon atoms.
• the alkylamino group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.
• the anilino group represented by R 3 and R 4 in formula (1) is preferably an anilino group having 6 to 40 carbon atoms, more preferably an anilino group having 6 to 30 carbon atoms, and an anilino group having 6 to 30 carbon atoms.
• An anilino group having 20 carbon atoms is more preferred, an anilino group having 6 to 15 carbon atoms is particularly preferred, and an anilino group having 6 to 12 carbon atoms is most preferred.
• the anilino group may have a substituent. Examples of the substituent include the groups described for the substituent T described later.
• the acylamino group represented by R 3 and R 4 in formula (1) is preferably an acylamino group having 2 to 30 carbon atoms, more preferably an acylamino group having 2 to 20 carbon atoms, and more preferably an acylamino group having 2 to 15 carbon atoms. is more preferred, and an acylamino group having 2 to 10 carbon atoms is particularly preferred.
• the acylamino group may have a substituent. Examples of the substituent include the groups described for the substituent T described later.
• the alkylsulfonylamino group represented by R 3 and R 4 in formula (1) is preferably an alkylsulfonylamino group having 2 to 30 carbon atoms, more preferably an alkylsulfonylamino group having 2 to 20 carbon atoms. , more preferably an alkylsulfonylamino group having 2 to 15 carbon atoms, particularly preferably an alkylsulfonylamino group having 2 to 10 carbon atoms.
• the alkylsulfonylamino group may have a substituent. Examples of the substituent include the groups described for the substituent T described later.
• the arylsulfonylamino group represented by R 3 and R 4 in formula (1) is preferably an arylsulfonylamino group having 6 to 40 carbon atoms, more preferably an arylsulfonylamino group having 6 to 30 carbon atoms. , more preferably an arylsulfonylamino group having 6 to 20 carbon atoms, particularly preferably an arylsulfonylamino group having 6 to 15 carbon atoms, most preferably an arylsulfonylamino group having 6 to 12 carbon atoms. preferable.
• the arylsulfonylamino group may have a substituent. Examples of the substituent include the groups described for the substituent T described later.
• the alkylthio group represented by R 3 and R 4 in formula (1) is preferably an alkylthio group having 1 to 30 carbon atoms, more preferably an alkylthio group having 1 to 20 carbon atoms, and more preferably an alkylthio group having 1 to 15 carbon atoms. is more preferred, an alkylthio group having 1 to 10 carbon atoms is particularly preferred, and an alkylthio group having 1 to 8 carbon atoms is most preferred.
• Alkylthio groups may be linear or branched.
• the alkylthio group may have a substituent. Examples of the substituent include the groups described for the substituent T described later.
• the arylthio group represented by R 3 and R 4 in formula (1) is preferably an arylthio group having 6 to 40 carbon atoms, more preferably an arylthio group having 6 to 30 carbon atoms, and more preferably an arylthio group having 6 to 20 carbon atoms. is more preferred, an arylthio group having 6 to 15 carbon atoms is particularly preferred, and an arylthio group having 6 to 12 carbon atoms is most preferred.
• the arylthio group may have a substituent. Examples of the substituent include the groups described for the substituent T described later.
• the ethylenically unsaturated bond-containing groups represented by R 3 and R 4 of formula (1) include the ethylenically unsaturated bond-containing groups represented by R 1 and R 2 of formula (1), and R of formula (2)
• the groups described as the ethylenically unsaturated bond-containing groups represented by 11 and R 12 can be mentioned.
• At least one of R3 and R4 in formula (1) is a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylamino group, anilino group, an acylamino group, an alkylsulfonylamino group, or an aryl It is a sulfonylamino group, an alkylthio group, an arylthio group, or an ethylenically unsaturated bond-containing group, and is preferably an alkyl group, an alkoxy group, or an aryloxy group because it can further suppress precipitation after kneading with a polymer compound. preferable.
• one of R 3 and R 4 is a hydrogen atom, and the other is a halogen atom, an alkyl group, an aryl group, or a An alkoxy group, an aryloxy group, an acyloxy group, an alkylamino group, anilino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, or an ethylenically unsaturated bond-containing group is preferred, and R It is more preferable that one of R3 and R4 is a hydrogen atom and the other is an alkyl group , an alkoxy group or an aryloxy group , and one of R3 and R4 is a hydrogen atom and the other is an alkyl group. is more preferred.
• R 1 and R 3 in formula (1) may combine to form a ring
• R 3 and R 4 may combine to form a ring
• R 2 and R 4 may combine
• a ring may be formed.
• the ring formed by combining these groups is preferably a 5- or 6-membered ring.
• the formed ring may have a substituent. Examples of the substituent include the groups described for the substituent T described later.
• Examples of the substituents represented by R 5 and R 6 in formula (1) and R 13 , R 14 , R 15 and R 16 in formula (2) include the groups described below for the substituent T, and alkyl is preferably an aryl group or a heterocyclic group, more preferably an alkyl group or an aryl group, and even more preferably an alkyl group.
• the alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, even more preferably an alkyl group having 1 to 15 carbon atoms.
• An alkyl group having 1 to 10 carbon atoms is particularly preferred, and an alkyl group having 1 to 8 carbon atoms is most preferred.
• the alkyl group may be linear, branched or cyclic, preferably linear or branched.
• the alkyl group may have a substituent. Examples of the substituent include the groups described for the substituent T described later.
• the aryl group is preferably an aryl group having 6 to 40 carbon atoms, more preferably an aryl group having 6 to 30 carbon atoms, even more preferably an aryl group having 6 to 20 carbon atoms.
• An aryl group having 6 to 15 carbon atoms is particularly preferred, and an aryl group having 6 to 12 carbon atoms is most preferred.
• the aryl group is preferably a phenyl group and a naphthyl group, more preferably a phenyl group.
• the aryl group may have a substituent. Examples of the substituent include the groups described for the substituent T described later.
• the heterocyclic ring in the heterocyclic group preferably contains a 5- or 6-membered saturated or unsaturated heterocyclic ring.
• the heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring.
• the heteroatoms that make up the ring of the heterocyclic ring include B, N, O, S, Se and Te, with N, O and S being preferred.
• a heterocycle preferably has a free valency (monovalence) at its carbon atoms (the heterocyclic group is attached at a carbon atom).
• the number of carbon atoms in the heterocyclic group is preferably 1-40, more preferably 1-30, still more preferably 1-20.
• Examples of saturated heterocyclic rings in heterocyclic groups include pyrrolidine ring, morpholine ring, 2-bora-1,3-dioxolane ring and 1,3-thiazolidine ring.
• Examples of unsaturated heterocyclic rings in heterocyclic groups include imidazole, thiazole, benzothiazole, benzoxazole, benzotriazole, benzoselenazole, pyridine, pyrimidine and quinoline rings.
• the heterocyclic group may have a substituent. Examples of the substituent include the groups described for the substituent T described later.
• R 5 and R 6 in formula (1) may combine to form a ring
• R 13 and R 14 in formula (2) may combine to form a ring
• R 15 and R 16 of may combine to form a ring.
• the ring formed by combining these groups is preferably a 5- or 6-membered ring. Specific examples of rings include hexahydropyridazine ring, tetrahydropyridazine ring, tetrahydrophthalazine ring and the like.
• the formed ring may have a substituent. Examples of the substituent include the groups described for the substituent T described later.
• R 5 and R 6 of formula (1) and R 13 , R 14 , R 15 and R 16 of formula (2) are each independently a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; is preferred, an alkyl group or an aryl group is more preferred, and an alkyl group is even more preferred.
• Substituent T includes the following groups. halogen atoms (e.g., chlorine atoms, bromine atoms, iodine atoms); Alkyl groups [linear, branched, and cyclic alkyl groups.
• halogen atoms e.g., chlorine atoms, bromine atoms, iodine atoms
• Alkyl groups [linear, branched, and cyclic alkyl groups.
• linear or branched alkyl groups preferably linear or branched alkyl groups having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n -octyl group, eicosyl group, 2-chloroethyl group, 2-cyanoethyl group, 2-ethylhexyl group
• cycloalkyl group preferably a cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl group, cyclopentyl group, 4- n-dodecylcyclohexyl group
• bicycloalkyl group preferably a bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms.
• alkyl group for example, an alkylthio group alkyl group
• Alkenyl groups [linear, branched, and cyclic alkenyl groups.
• linear or branched alkenyl groups preferably linear or branched alkenyl groups having 2 to 30 carbon atoms, such as vinyl group, allyl group, prenyl group, geranyl group, oleyl group
• cycloalkenyl groups Preferably, a cycloalkenyl group having 3 to 30 carbon atoms. That is, a monovalent group obtained by removing one hydrogen atom from a cycloalkene having 3 to 30 carbon atoms.
• bicycloalkenyl group preferably a bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkene having one double bond.
• bicyclo[2,2,1]hept-2-en-1-yl group bicyclo[2,2,2]oct-2-en-4-yl group).
• an alkynyl group preferably a linear or branched alkynyl group having 2 to 30 carbon atoms, such as an ethynyl group or a propargyl group
• an aryl group preferably an aryl group having 6 to 30 carbon atoms, such as a phenyl group, p-tolyl group, naphthyl group, m-chlorophenyl group, o-hexadecanoylaminophenyl group
• Heterocyclic group preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered aromatic or non-aromatic heterocyclic compound, more preferably a 5- or 6-membered group having 1 to 20 carbon atoms (for example, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group); cyano group; hydroxy group; nitro group; Carboxyl group; an alkoxy group (preferably a linear or branched alkoxy group having 1 to 30 carbon atoms, such as a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, an n-
• Examples include phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group ); a heterocyclic oxy group (preferably a heterocyclic oxy group having 2 to 30 carbon atoms, such as a 1-phenyltetrazole-5-oxy group and a 2-tetrahydropyranyloxy group); Acyloxy group (preferably formyloxy group, alkylcarbonyloxy group having 2 to 30 carbon atoms, arylcarbonyloxy group having 6 to 30 carbon atoms. For example, formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group);
• Carbamoyloxy group (preferably a carbamoyloxy group having 1 to 30 carbon atoms.
• Examples include formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoyl amino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group);
• aminocarbonylamino group preferably an aminocarbonylamino group having 1 to 30 carbon atoms.
• carbamoylamino group N,N-dimethylaminocarbonylamino group, N,N-diethylaminocarbonylamino group, morpholinocarbonylamino group
• An alkoxycarbonylamino group preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms.
• methoxycarbonylamino group methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxy carbonylamino group
• an aryloxycarbonylamino group preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms, such as a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, a mn-octyloxyphenoxycarbonylamino group
• sulfamoylamino group preferably a sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino group, N,N-dimethylaminosulfonylamino group, Nn-octylaminosulfonylamino group
• a sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms; for example, N-ethylsulfamoyl group, N-(3-dodecyloxypropyl)sulfamoyl group, N,N-dimethylsulfamoyl group, N-acetylsulfamoyl group; famoyl group, N-benzoylsulfamoyl group, N-(N'-phenylcarbamoyl)sulfamoyl group); sulfo group; an alkyl or arylsulfinyl group (preferably an alkylsulfinyl group having 1 to 30 carbon atoms, an arylsulfinyl group having 6 to 30 carbon atoms, such as a methylsulfinyl group, an ethylsulfinyl group, a phenyl
• an acyl group (preferably a formyl group, an alkylcarbonyl group having 2 to 30 carbon atoms, an arylcarbonyl group having 7 to 30 carbon atoms, or a heterocyclic carbonyl group bonded to a carbonyl group via a carbon atom having 4 to 30 carbon atoms; for example, , acetyl group, pivaloyl group, 2-chloroacetyl group, stearoyl group, benzoyl group, pn-octyloxyphenylcarbonyl group, 2-pyridylcarbonyl group, 2-furylcarbonyl group); an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms, such as a phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, pt-butylphenoxycarbonyl group); An alkoxycarbonyl group (preferably an alk
• methoxycarbonyl group ethoxycarbonyl group, t-butoxycarbonyl group, n-octadecyloxycarbonyl group, n-butoxycarbonyl group, 2-ethyl xyloxycarbonyl group
• Carbamoyl group preferably a carbamoyl group having 1 to 30 carbon atoms.
• Examples include carbamoyl group, N-methylcarbamoyl group, N,N-dimethylcarbamoyl group, N,N-di-n-octylcarbamoyl group, N-(methyl sulfonyl) carbamoyl group); Aryl or heterocyclic azo groups (preferably aryl azo groups having 6 to 30 carbon atoms, heterocyclic azo groups having 3 to 30 carbon atoms.
• phenylazo group p-chlorophenylazo group, 5-ethylthio-1,3,4- thiadiazol-2-ylazo group
• imide group preferably N-succinimide group, N-phthalimide group
• a phosphino group preferably a phosphino group having 2 to 30 carbon atoms, such as a dimethylphosphino group, a diphenylphosphino group, a methylphenoxyphosphino group
• a phosphinyl group preferably a phosphinyl group having 2 to 30 carbon atoms, such as a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group
• a phosphinyloxy group preferably a phosphinyloxy group having 2 to 30 carbon atoms, such as a diphenoxyphosphinyloxy group and a dioctyloxypho
• one or more hydrogen atoms may be substituted with the substituent T described above.
• substituents include alkylcarbonylaminosulfonyl groups, arylcarbonylaminosulfonyl groups, alkylsulfonylaminocarbonyl groups, and arylsulfonylaminocarbonyl groups. Specific examples include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, a benzoylaminosulfonyl group and the like.
• the maximum absorption wavelength of the specific compound preferably exists in the wavelength range of 360 to 430 nm, more preferably in the wavelength range of 370 to 420 nm, even more preferably in the wavelength range of 380 to 420 nm. It is particularly preferred to be present in the wavelength range of ⁇ 405 nm.
• the molar extinction coefficient of the specific compound at the maximum absorption wavelength is preferably 10,000 L/mol ⁇ cm or more, more preferably 20,000 L/mol ⁇ cm or more, and even more preferably 30,000 L/mol ⁇ cm or more. Further, the molar extinction coefficient of the specific compound at a wavelength of 400 nm is preferably 1000 L/mol ⁇ cm or more, more preferably 3000 L/mol ⁇ cm or more, and even more preferably 5000 L/mol ⁇ cm or more.
• the maximum absorption wavelength and molar extinction coefficient of a specific compound can be determined by measuring the spectrum of a solution prepared by dissolving the specific compound in ethyl acetate using a 1 cm quartz cell at room temperature (25°C).
• Examples of the measuring device include UV-1800PC (manufactured by Shimadzu Corporation).
• the specific compound can be produced according to the methods described in JP-A-2009-067984, JP-A-2009-263616, JP-A-2009-263617, and International Publication No. 2017/122503.
• Specific examples of the specific compound include compounds having the following structures.
• Me is a methyl group
• Et is an ethyl group
• Pr is a propyl group
• Bu is a butyl group
• tBu is a tert-butyl group
• Ph is a phenyl group.
• the ultraviolet absorber used in the kneaded material of the present invention may contain compound A having a maximum absorption wavelength on the shorter wavelength side than the specific compound described above.
• the maximum absorption wavelength of compound A is preferably in the wavelength range of 300 to 380 nm, more preferably in the wavelength range of 300 to 370 nm, still more preferably in the wavelength range of 310 to 360 nm, and the wavelength is 310 nm. It is particularly preferred to be present in the range of ⁇ 350 nm. According to this aspect, it is possible to form a molded article or the like that can block light of wavelengths in the ultraviolet region over a wide range.
• the difference between the maximum absorption wavelength of the specific compound and the maximum absorption wavelength of compound A is preferably 1 to 70 nm, more preferably 10 to 60 nm, even more preferably 20 to 50 nm. According to this aspect, it is possible to form a molded article capable of shielding a wide range of light having a wavelength in the ultraviolet region.
• Compound A includes aminobutadiene compounds, dibenzoylmethane compounds, benzotriazole compounds, triazine compounds, benzophenone compounds, and acrylate compounds. At least one compound selected from benzotriazole compounds, triazine compounds and benzophenone compounds is preferable because it is easy to suppress precipitation and the like.
• compound A examples include compounds having the following structures.
• Compound A is JP 2003-128730, JP 2003-129033, JP 2014-077076, JP 2015-164994, JP 2015-168822, JP 2018-135282 Publications, JP 2018-168089, JP 2018-168278, JP 2018-188589, JP 2019-001767, JP 2020-023697, JP 2020-041013, Patent No. 5518613, Patent No. 5868465, Patent No. 6301526, Patent No. 6354665, Special Table 2017-503905, International Publication No. 2015/064674, International Publication No.
• the content of the ultraviolet absorber is preferably 0.0005 to 20 parts by mass with respect to 100 parts by mass of the polymer compound.
• the lower limit is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more.
• the upper limit is preferably 10 parts by mass or less, more preferably 2 parts by mass or less.
• the content of the ultraviolet absorber is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the polymer compound.
• the lower limit is preferably 2 parts by mass or more, more preferably 5 parts by mass or more.
• the upper limit is preferably 30 parts by mass or less, more preferably 20 parts by mass or less.
• the content of the specific compound is preferably 0.0005 to 20 parts by mass with respect to 100 parts by mass of the polymer compound.
• the lower limit is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more.
• the upper limit is preferably 10 parts by mass or less, more preferably 2 parts by mass or less.
• the content of the specific compound is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the polymer compound.
• the lower limit is preferably 2 parts by mass or more, more preferably 5 parts by mass or more.
• the upper limit is preferably 30 parts by mass or less, more preferably 20 parts by mass or less.
• the kneaded material may contain only 1 type of specific compounds, and may contain 2 or more types. When two or more specific compounds are included, the total amount thereof is preferably within the above range. Further, when the specific compound and the compound A described above are used together as an ultraviolet absorber, the content of the compound A is preferably 5 to 1000 parts by weight with respect to 100 parts by weight of the specific compound, and 10 to 700 parts by weight. It is more preferably 20 to 500 parts by mass.
• the kneaded material may contain only 1 type of compound A, and may contain 2 or more types. When two or more compounds A are included, the total amount thereof is preferably within the above range.
• the kneaded material of the present invention contains a polymer compound.
• the weight average molecular weight of the polymer compound is preferably 3,000 to 2,000,000.
• the lower limit of the weight average molecular weight of the polymer compound is preferably 5000 or more.
• the upper limit of the weight average molecular weight of the polymer compound is preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 200,000 or less.
• the weight average molecular weight of a polymer compound is a value measured by gel permeation chromatography (GPC). Measurement by GPC uses HLC (registered trademark)-8020GPC (manufactured by Tosoh Corporation) as a measuring device, and TSKgel (registered trademark) Super Multipore HZ-H (4.6 mm ID ⁇ 15 cm, Tosoh Corporation) as a column. ), and THF (tetrahydrofuran) is used as the eluent.
• the measurement conditions are a sample concentration of 0.45% by mass, a flow rate of 0.35 ml/min, a sample injection volume of 10 ⁇ l, a measurement temperature of 40° C., and an RI detector.
• the calibration curve is "Standard sample TSK standard, polystyrene" of Tosoh Corporation: "F-40", “F-20”, “F-4", “F-1”, “A-5000”, “A -2500”, “A-1000”, and "n-propylbenzene”.
• the glass transition point of the polymer compound is preferably -80°C or higher and 200°C or lower.
• the glass transition point of the polymer compound is preferably ⁇ 30° C. or higher.
• the glass transition point of the polymer compound is preferably 180° C. or lower. If the glass transition point of the polymer compound is within the above range, it has appropriate softness and strength, and is excellent in compatibility with the ultraviolet absorber.
• the total light transmittance of the polymer compound is preferably 80% or higher, more preferably 85% or higher, and even more preferably 90% or higher.
• the total light transmittance of the polymer compound was measured based on the content described in "4th Edition Experimental Chemistry Course 29 Polymer Materials” (Maruzen, 1992) edited by The Chemical Society of Japan, pp. 225-232. value.
• the polymer compound is preferably a resin.
• the resin may be a thermoplastic resin or a thermosetting resin.
• a thermoplastic resin is preferable from the viewpoint of kneadability with the ultraviolet absorber and ease of processing into a molded article.
• resins include (meth) acrylic resins, ene-thiol resins, polyester resins, polycarbonate resins, vinyl polymers [e.g., polydiene resins, polyalkene resins, polystyrene resins, polyvinyl ether resins, polyvinyl alcohol resins, polyvinyl ketone resins, polyfluoro vinyl resins and polyvinyl bromide resins], polythioether resins, polyphenylene resins, polyurethane resins, polysulfonate resins, nitrosopolymer resins, polysiloxane resins, polysulfide resins, polythioester resins, polysulfone resins, polysulfonamide resin
• (Meth)acrylic resins include polymers containing structural units derived from (meth)acrylic acid and/or esters thereof. Specific examples include polymers obtained by polymerizing at least one compound selected from the group consisting of (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylamide, and (meth)acrylonitrile. be done.
• Polyester resins include polyols (e.g., ethylene glycol, propylene glycol, glycerin, and trimethylolpropane), polybasic acids (e.g., aromatic dicarboxylic acids (e.g., terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, etc.), and dicarboxylic acids in which the hydrogen atoms of these aromatic rings are substituted with methyl group, ethyl group, phenyl group, etc.), aliphatic dicarboxylic acids having 2 to 20 carbon atoms (e.g.
• polyester resins include polyethylene terephthalate and polyethylene naphthalate.
• epoxy resins examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, and aliphatic epoxy resin.
• Commercially available epoxy resins may be used, and examples of commercially available products include the following.
• Examples of commercially available bisphenol A type epoxy resins include jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, and jER1010 (manufactured by Mitsubishi Chemical Corporation), and EPICLON860, EPICLON1050, EPICLON1051, and EPICLON1055 (manufactured by DIC Corporation) and the like.
• Examples of commercially available bisphenol F type epoxy resins include jER806, jER807, jER4004, jER4005, jER4007, and jER4010 (manufactured by Mitsubishi Chemical Corporation), EPICLON830, and EPICLON835 (manufactured by DIC Corporation), and LCE-21 and RE-602S (manufactured by Nippon Kayaku Co., Ltd.).
• Examples of commercially available phenolic novolac epoxy resins include jER152, jER154, jER157S70, and jER157S65 (manufactured by Mitsubishi Chemical Corporation), and EPICLON N-740, EPICLON N-770, and EPICLON N-775 ( and the like, manufactured by DIC Corporation).
• Examples of commercially available cresol novolak epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, and EPICLON N-695 (the above , manufactured by DIC Corporation), and EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.).
• Examples of commercially available aliphatic epoxy resins include ADEKA RESIN EP series (eg EP-4080S, EP-4085S, and EP-4088S; manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, and Celoxide 2085. , EHPE3150, EPOLEAD PB 3600, and EPOLEAD PB 4700 (manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, and EX-850L (manufactured by Nagase ChemteX ( manufactured by ADEKA Corporation), ADEKA RESIN EP series (e.g.
• EP-4000S, EP-4003S, EP-4010S, and EP-4011S manufactured by ADEKA Corporation
• NC-2000, NC-3000, NC-7300, XD -1000, EPPN-501, and EPPN-502 manufactured by ADEKA Corporation
• jER1031S manufactured by Mitsubishi Chemical Corporation
• Other examples of commercially available epoxy resins include Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (manufactured by NOF Corporation, epoxy group-containing polymer).
• cellulose acylate resin cellulose acylates described in paragraphs 0016 to 0021 of JP-A-2012-215689 are preferably used.
• polyester resin commercially available products such as Vylon series manufactured by Toyobo Co., Ltd. (eg, Vylon 500) can also be used.
• Vylon series manufactured by Toyobo Co., Ltd.
• SK Dyne series eg, SK Dyne-SF2147, etc.
• Soken Chemical Co., Ltd. can also be used.
• the polystyrene resin is preferably a resin containing 50% by mass or more of repeating units derived from a styrene-based monomer, more preferably a resin containing 70% by mass or more of repeating units derived from a styrene-based monomer. More preferably, the resin contains 85% by mass or more of repeating units derived from a monomer.
• styrene-based monomers include styrene and its derivatives.
• the styrene derivative is a compound in which another group is bonded to styrene, and examples thereof include o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, o-ethylstyrene, Alkyl styrenes such as p-ethylstyrene, and hydroxy, alkoxy and carboxyl groups on the benzene nucleus of styrene such as hydroxystyrene, tert-butoxystyrene, vinyl benzoic acid, o-chlorostyrene and p-chlorostyrene. , substituted styrene into which a halogen or the like is introduced, and the like.
• the polystyrene resin may contain repeating units derived from monomers other than styrene-based monomers.
• Other monomers include alkyl (meth)acrylates such as methyl (meth)acrylate, cyclohexyl (meth)acrylate, methylphenyl (meth)acrylate, and isopropyl (meth)acrylate; methacrylic acid, acrylic acid, itaconic acid, maleic acid, Unsaturated carboxylic acid monomers such as fumaric acid and cinnamic acid; unsaturated dicarboxylic acid anhydride monomers such as maleic anhydride, itaconic acid, ethyl maleic acid, methyl itaconic acid and chloromaleic acid; acrylonitrile, methacrylonitrile unsaturated nitrile monomers such as; and the like.
• polystyrene resins include AS-70 (acrylonitrile/styrene copolymer resin, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and SMA2000P (styrene/maleic acid copolymer, Kawakuro Kagaku Co., Ltd.).
• Polycarbonate resins include reaction products of polyhydric phenols and phosgene or carbonate esters.
• polyhydric phenols examples include hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxy phenyl)-1-phenylethane, bisphenol A, bisphenol C, bisphenol E, bisphenol F, bisphenol M, bisphenol P, bisphenol S, bisphenol Z, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1 , 1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane, 2,2- bis(4-hydroxyphenyl)butane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 4,
• Carbonic acid esters include bisalkyl carbonate and bisaryl carbonate. Specific examples include diphenyl carbonate, bis(chlorophenyl) carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like, with bis(diphenyl) carbonate, dimethyl carbonate and diethyl carbonate being preferred. .
• polycarbonate resin Commercially available products of polycarbonate resin include the SD Polyca series manufactured by Sumika Polycarbonate Co., Ltd.
• thiourethane resins include reaction products of isocyanate compounds and polythiol compounds, reaction products of thiourethane resin precursors, and the like.
• Commercially available thiourethane resin precursors include MR-7, MR-8, MR-10 and MR-174 manufactured by Mitsui Chemicals, Inc.
• polyamide resins include aliphatic polyamide resins and aromatic polyamide resins.
• aliphatic polyamide resins include nylon 6, nylon 11, nylon 12, nylon 46, nylon 66, nylon 666, nylon 610 and nylon 612.
• aromatic polyamide resins include resins polymerized by dehydration condensation of diamines and dicarboxylic acids and using at least one of diamines and dicarboxylic acids containing an aromatic ring.
• Specific examples of aromatic polyamide resins include condensation polymers of meta-xylylenediamine and adipic acid or adipic acid halide.
• the cyclic olefin resin (1) a polymer containing a structural unit derived from a norbornene compound, (2) a polymer containing a structural unit derived from a monocyclic cyclic olefin compound other than a norbornene compound, (3) a cyclic conjugated A polymer containing a structural unit derived from a diene compound, (4) a polymer containing a structural unit derived from a vinyl alicyclic hydrocarbon compound, and a structural unit derived from each compound of (1) to (4) hydrides of polymers containing
• the polymer containing a structural unit derived from a norbornene compound and the polymer containing a structural unit derived from a monocyclic cyclic olefin compound include ring-opened polymers of each compound.
• a hydride of a polymer of a norbornene compound can be synthesized by addition polymerization or ring-opening metathesis polymerization of a norbornene compound or the like, followed by hydrogenation. Synthesis methods, for example, JP-A-01-240517, JP-A-07-196736, JP-A-60-026024, JP-A-62-019801, JP-A-2003-159767 and JP-A-2003-159767 It is described in each publication such as Japanese Patent Publication No. 2004-309979.
• cyclic olefin resins include ARTON series manufactured by JSR (for example, ARTON G, ARTON F, ARTON RX4500, etc.), Zeonor ZF14, ZF16, Zeonex 250 and Zeonex 280 manufactured by Nippon Zeon. etc.
• the resin may be an alkali-soluble resin.
• Alkali-soluble resins include resins having acid groups. Examples of acid groups include carboxyl groups, phosphoric acid groups, sulfonic acid groups, and phenolic hydroxy groups. Only one type of acid group may be used, or two or more types may be used.
• the alkali-soluble resin is preferably one that is soluble in an organic solvent and can be developed with a weakly alkaline aqueous solution.
• alkali-soluble resins include polymers having carboxyl groups in side chains, such as JP-A-59-044615, JP-B-54-034327, JP-B-58-012577, JP-B-54-025957.
• alkali-soluble resin a resin obtained by adding an acid anhydride to a polymer having a hydroxyl group is also useful.
• the alkali-soluble resin may be a resin obtained by copolymerizing a hydrophilic monomer.
• Hydrophilic monomers include alkoxyalkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, glycerol (meth)acrylates, (meth)acrylamides, N-methylolacrylamides, secondary or tertiary alkylacrylamides, dialkylaminoalkyl (meth)acrylate, morpholine (meth)acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth)acrylate, ethyl (meth)acrylate, branched or linear propyl (meth)acrylate, Branched or linear butyl (meth)acrylate, phenoxyhydroxypropyl (meth)acrylate, and the like can be mentioned.
• hydrophilic monomers include a tetrahydrofurfuryl group, a phosphate group, a phosphate ester group, a quaternary ammonium base, an ethyleneoxy chain, a propyleneoxy chain, a sulfonic acid group and a group derived from a salt thereof, and a morpholinoethyl group. Also useful are monomers such as
• the alkali-soluble resin may have ethylenically unsaturated bond-containing groups such as vinyl groups, styrene groups, allyl groups, methallyl groups, and (meth)acryloyl groups, in order to improve cross-linking efficiency.
• ethylenically unsaturated bond-containing groups such as vinyl groups, styrene groups, allyl groups, methallyl groups, and (meth)acryloyl groups, in order to improve cross-linking efficiency.
• alkali-soluble resins having ethylenically unsaturated bond-containing groups include Dianal BR series (polymethyl methacrylate (PMMA), such as Dianal BR-80, BR-83, and BR-87; Mitsubishi Chemical ( Co., Ltd.), Photomer 6173 (carboxyl group-containing polyurethane acrylic oligomer; Diamond Shamrock Co., Ltd.), Viscoat R-264, and KS Resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cychromer P series ( For example, ACA230AA), Plaxel CF200 series (both manufactured by Daicel Corporation), Ebecryl3800 (manufactured by Daicel UCB Corporation), and Acrycure-RD-F8 (manufactured by Nippon Shokubai Co., Ltd.).
• PMMA polymethyl methacrylate
• Mitsubishi Chemical Co., Ltd.
• Photomer 6173 carboxyl group-containing polyurethane acrylic oligomer
• polyhydroxystyrene resins, (meth)acrylic resins, polystyrene resins, and polysiloxane resins are preferred from the viewpoint of heat resistance, and (meth)acrylic resins are preferred from the viewpoint of control of developability. more preferred.
• the weight average molecular weight of the alkali-soluble resin is preferably 3,000 to 200,000, more preferably 5,000 to 50,000.
• the acid value of the alkali-soluble resin is preferably 30-200 mgKOH/g.
• the lower limit of the acid value is preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g or more.
• the upper limit of the acid value is preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less.
• the content of the polymer compound in the kneaded product is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.
• the upper limit can be, for example, 99% by mass or less.
• the kneaded material may contain only one polymer compound, or may contain two or more polymer compounds. When two or more types of polymer compounds are included, the total amount thereof is preferably within the above range.
• the kneaded product of the present invention can contain a plasticizer.
• a plasticizer By containing a plasticizer, the physical properties of the polymer compound are adjusted, and the effect of improving compatibility control and stability (particularly light fastness) can be obtained.
• plasticizers include phthalate plasticizers, phosphate ester plasticizers, trimellitate ester plasticizers, fatty acid ester plasticizers, polyester plasticizers, glycerin plasticizers, polyalkylene glycol plasticizers, and the like. and phthalate ester plasticizers and phosphate ester plasticizers are preferred from the viewpoint of compatibility with polymer compounds.
• Phthalate plasticizers include dimethyl phthalate, diethyl phthalate, diisopropyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dicyclohexyl phthalate, diphenyl phthalate, bis(2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate and the like.
• Phosphate ester plasticizers include trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, and tricresyl phosphate.
• Trimellitate ester plasticizers include tributyl trimetate and tris(2-ethylhexyl) trimetate.
• Fatty acid ester plasticizers include dimethyl adipate, diethyl adipate, dipropyl adipate, diisopropyl adipate, dibutyl adipate, diisobutyl adipate, dimethyl dodecanoate, dibutyl maleate, and ethyl oleate.
• Polyester-based plasticizers include acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, and rosin, and propylene glycol, 1,3-butanediol, and 1,4-butanediol. , 1,6-hexanediol, ethylene glycol and diethylene glycol, and polyesters with hydroxycarboxylic acids such as polycaprolactone. These polyesters may be terminal-blocked with a monofunctional carboxylic acid or monofunctional alcohol, or may be terminal-blocked with an epoxy compound or the like.
• Glycerin-based plasticizers include glycerin monoacetomonolaurate, glycerin diacetomonolaurate, glycerin monoacetomonostearate, glycerin diacetomonooleate and glycerin monoacetomonomontanate.
• polyalkylene glycol-based plasticizers include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide addition polymers of bisphenols, propylene oxide addition polymers of bisphenols, and tetrahydrofuran addition polymers of bisphenols. Terminal epoxy-modified compounds, terminal ester-modified compounds, terminal ether-modified compounds, and the like can be mentioned.
• the molecular weight of the plasticizer is preferably less than 3,000, more preferably 2,000 or less, and even more preferably 1,500 or less.
• the content of the plasticizer in the kneaded product is preferably 0.001 to 30% by mass.
• the lower limit is preferably 0.005% by mass or more, more preferably 0.01% by mass or more.
• the upper limit is preferably 20% by mass or less, more preferably 10% by mass or less.
• the content of the plasticizer in the kneaded product is preferably 0.001 to 30 parts by mass with respect to 100 parts by mass of the polymer compound.
• the lower limit is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more.
• the upper limit is preferably 20 parts by mass or less, more preferably 10 parts by mass or less.
• the kneaded product may contain only one plasticizer, or may contain two or more plasticizers. When two or more plasticizers are included, the total amount thereof is preferably within the above range.
• the kneaded product of the present invention can contain a polymerizable monomer.
• the polymerizable monomer is preferably a compound having an ethylenically unsaturated bond-containing group, more preferably a compound having two or more ethylenically unsaturated bond-containing groups.
• the upper limit of the number of ethylenically unsaturated bond-containing groups contained in the polymerizable monomer is preferably 15 or less, more preferably 10 or less, and even more preferably 6 or less.
• a vinyl group, an allyl group, a (meth)acryloyl group, etc. are mentioned as an ethylenically unsaturated bond containing group which a polymerizable compound has.
• the molecular weight of the polymerizable monomer is preferably 100-2000.
• the upper limit is preferably 1500 or less, more preferably 1000 or less.
• the lower limit is more preferably 150 or more, even more preferably 250 or more.
• the polymerizable monomer is preferably a (meth)acrylate compound, more preferably a bifunctional or higher (meth)acrylate compound, still more preferably a di- to fifteen-functional (meth)acrylate compound, and 2 A to 10-functional (meth)acrylate compound is more preferred, and a di- to hexa-functional (meth)acrylate compound is particularly preferred.
• polymerizable monomers include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri((meth)acryloyloxy ethyl) isocyanurate, pentaerythritol tetra(meth)acrylate ethylene oxide EO (ethylene oxide) modified, dipentaerythritol hexa(meth)acrylate EO (ethylene oxide) modified, benzyl (meth)acrylate and the like.
• polymerizable monomers include Nippon Kayaku Co., Ltd.'s KAYARAD series (e.g., D-330, D-320, D-310, PET-30, TPA-330, DPHA, etc.), Shin-Nakamura Chemical Industry ( Co., Ltd. NK ester series (eg A-DPH-12E, A-TMMT, A-TMM-3 etc.), Kyoeisha Chemical Co., Ltd. light acrylate series (eg DCP-A etc.), Toagosei Co., Ltd. Aronix series manufactured by Osaka Organic Chemical Industry Co., Ltd. (eg, V #802, etc.) polyfunctional (meth)acrylate compounds.
• KAYARAD series e.g., D-330, D-320, D-310, PET-30, TPA-330, DPHA, etc.
• Shin-Nakamura Chemical Industry Co., Ltd. NK ester series (eg A-DPH-12E, A-TMMT, A-TMM-3 etc
• Polymerizable monomers include (meth)acrylate compounds described in JP-A-48-064183, JP-B-49-043191, JP-B-52-030490; 20, No. 7, 300-308 (1984) as photocurable monomers and oligomers can be used.
• the content of the polymerizable monomer in the kneaded product is preferably 1 to 20% by mass.
• the lower limit is preferably 2% by mass or more.
• the upper limit is preferably 10% by mass or less.
• the kneaded product may contain only one type of polymerizable monomer, or may contain two or more types. When two or more polymerizable monomers are included, the total amount thereof is preferably within the above range.
• the kneaded product of the present invention can contain a polymerization initiator.
• a polymerization initiator a compound capable of generating an initiation species necessary for the polymerization reaction upon application of energy can be used.
• the polymerization initiator can be appropriately selected from, for example, photopolymerization initiators and thermal polymerization initiators.
• photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, thio compounds. , ketone compounds, aromatic onium salts, aminoacetophenone compounds, hydroxyacetophenone compounds, and the like.
• aminoacetophenone compounds include aminoacetophenone-based initiators described in JP-A-2009-191179 and JP-A-10-291969.
• Acylphosphine compounds include acylphosphine-based initiators described in Japanese Patent No. 4225898.
• the photopolymerization initiator may be a synthetic product or a commercially available product.
• hydroxyacetophenone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (manufactured by IGM Resins B.V.).
• Commercially available aminoacetophenone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (manufactured by IGM Resins B.V.).
• Commercially available acylphosphine compounds include Omnirad 819 and Omnirad TPO (manufactured by IGM Resins B.V.).
• An oxime compound is preferable as the photopolymerization initiator.
• Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, and JP-A-2016-006475. Examples thereof include compounds described in paragraphs 0073 to 0075 of the publication.
• oxime compounds oxime ester compounds are preferred.
• Commercially available oxime compounds include Irgacure OXE01, Irgacure OXE02 (manufactured by BASF), and Irgacure OXE03 (manufactured by BASF).
• Thermal polymerization initiators include aromatic ketone compounds, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, and carbon halogens. A compound having a bond, an azo compound, and the like can be mentioned. Specific examples of thermal polymerization initiators include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.
• the content of the polymerization initiator in the kneaded product is preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the polymerizable monomer.
• the lower limit is preferably 0.05 parts by mass or more.
• the upper limit is preferably 10 parts by mass or less.
• the kneaded product may contain only one polymerization initiator, or may contain two or more polymerization initiators. When two or more polymerization initiators are included, the total amount thereof is preferably within the above range.
• a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups.
• the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and capable of forming a siloxane bond by at least one of hydrolysis reaction and condensation reaction.
• Hydrolyzable groups include, for example, halogen atoms, alkoxy groups, acyloxy groups and the like, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
• Examples of functional groups other than hydrolyzable groups include vinyl group, (meth)allyl group, (meth)acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group and isocyanate group. , phenyl group, etc., and amino group, (meth)acryloyl group and epoxy group are preferred.
• Specific examples of the silane coupling agent include compounds described in paragraph numbers 0018 to 0036 of JP-A-2009-288703 and compounds described in paragraph numbers 0056-0066 of JP-A-2009-242604. the contents of which are incorporated herein.
• Commercially available silane coupling agents include A-50 (organosilane) manufactured by Soken Chemical Co., Ltd., and the like.
• the content of the silane coupling agent in the kneaded product is preferably 0.1 to 5% by mass.
• the upper limit is preferably 3% by mass or less, more preferably 2% by mass or less.
• the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more.
• the kneaded material may contain only one type of silane coupling agent, or may contain two or more types. When two or more silane coupling agents are included, the total amount thereof is preferably within the above range.
• the kneaded product of the present invention can contain a surfactant.
• surfactants include surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362.
• a nonionic surfactant a fluorine-based surfactant, or a silicone-based surfactant is preferable.
• fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F -437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558 , F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-41, R-41-LM, R -01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (manufactured by DIC Corporation), Florard FC430, FC431, FC171 (manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104,
• an acrylic compound that has a molecular structure with a functional group containing a fluorine atom, and in which the functional group containing the fluorine atom is cleaved and the fluorine atom volatilizes when heat is applied is also suitable.
• a fluorosurfactant Megafac DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafac and DS-21.
• a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound is also preferably used as the fluorosurfactant.
• a block polymer can also be used for the fluorosurfactant.
• the fluorosurfactant has 2 or more (preferably 5 or more) repeating units derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group or a propyleneoxy group) (preferably 5 or more). ) and a repeating unit derived from an acrylate compound.
• a fluorine-containing polymer having an ethylenically unsaturated bond-containing group on the side chain can also be used as the fluorine-based surfactant.
• Commercially available products include Megafac RS-101, RS-102, RS-718K, and RS-72-K (manufactured by DIC Corporation).
• PFOA perfluorooctanoic acid
• PFOS perfluorooctane sulfonic acid
• silicone-based surfactants include straight-chain polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into side chains and terminals.
• Commercially available silicone-based surfactants include DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (toray ⁇ Dow Corning Co., Ltd.), X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF -643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (manufactured by Shin-Etsu Silicone Co., Ltd.
• Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester and the like.
• nonionic surfactants include Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF company), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D- 6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) and the like.
• the content of the surfactant in the kneaded product is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% by mass to 3.0% by mass.
• the kneaded material may contain only one type of surfactant, or may contain two or more types. When two or more surfactants are included, the total amount thereof is preferably within the above range.
• the kneaded product of the present invention may contain an organic solvent.
• organic solvents include alcohol-based solvents, ester-based solvents, ketone-based solvents, amide-based solvents, ether-based solvents, hydrocarbon-based solvents, and halogen-based solvents.
• organic solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, 2-ethoxyethanol, 2 - butoxyethanol, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, ethylene carbonate, N-methylpyrrolidone, dioxane, tetrahydrofuran, ethylene glycol dialkyl ether, propylene glycol dialkyl ether Ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, acetonitrile, propionitrile, benzonitrile, carboxylic acid ester, phosphoric acid ester, phosphonic acid ester, dimethylsulfoxide, sulfolane, dimethylformamide
• the content of the organic solvent in the kneaded product is preferably 0.1% by mass or less, more preferably 0.01% by mass or less. It is particularly preferred that the kneaded product of the present invention does not contain an organic solvent.
• the kneaded product of the present invention may optionally contain optional additives such as antioxidants, light stabilizers, processing stabilizers, anti-aging agents, polymerization inhibitors, flame retardants, and antistatic agents. good.
• the kneaded product of the present invention can also be suitably used in applications that may be exposed to sunlight or light including ultraviolet rays.
• Specific examples include coating materials or films for window glass of residences, facilities, transportation equipment, etc.; Precision machinery, electronic and electrical equipment, and parts for display devices; Containers or packaging materials for foods, chemicals, drugs, etc.; Sheets for agriculture and industry; Textile products and fibers for clothing such as sportswear, stockings, and hats; Plastic lenses, contact lenses , spectacles, artificial eyes and other lenses or their coating materials; optical supplies such as optical filters, prisms, mirrors and photographic materials; stationery such as tapes; Details of these can be referred to in paragraphs 0158 to 0218 of JP-A-2009-263617, the contents of which are incorporated herein.
• the kneaded product of the present invention can be preferably used for optical members and the like.
• it is preferably used as a kneaded product for ultraviolet cut filters, lenses or protective materials.
• the form of the protective material is not particularly limited, but may be a coating film form, a film form, a sheet form, or the like.
• the kneaded material of the present invention can also be used for various members of display devices.
• a liquid crystal display device it can be used for each member constituting the liquid crystal display device such as an antireflection film, a polarizing plate protective film, an optical film, a retardation film, an adhesive, and an adhesive.
• the method for producing the kneaded product of the present invention comprises an ultraviolet absorber containing at least one compound selected from the compounds represented by the above formula (1) and the compound represented by the formula (2), and a polymer compound. and a step of kneading (kneading step).
• the kneading step it is preferable to mix the ultraviolet absorber, the polymer compound, and, if necessary, other materials used for the kneaded product, and knead the resulting mixture.
• known devices such as a Banbury mixer, twin-screw extruder, single-screw extruder, rotor-type twin-screw kneader, and kneader can be used.
• the kneading temperature is preferably higher than the glass transition point of the polymer compound, more preferably higher than the glass transition point of the polymer compound.
• the kneaded material after the kneading step can be processed into a predetermined shape (for example, a pellet shape, etc.) as needed.
• the melted kneaded product can be molded into various shapes to form molded bodies.
• an unstretched resin film can be obtained by extruding a molten kneaded material through a die onto a cooling roll and cooling and solidifying it.
• Film molding that can be used to form the resin film includes T-die film molding, inflation molding, calender molding, and the like.
• the molded article of the present invention is obtained using the kneaded material of the present invention described above.
• the molded product of the present invention may be obtained by molding only the kneaded product of the present invention into a predetermined shape, and the kneaded product of the present invention, a polymer compound, and other additives are mixed to obtain a desired shape. It may be molded into a shape.
• the polymer compound include the materials described as the polymer compound used in the kneaded material of the present invention.
• Other additives include plasticizers, polymerizable monomers, polymerization initiators, silane coupling agents, surfactants, antioxidants, light stabilizers, processing stabilizers, anti-aging agents, polymerization inhibitors, flame retardants, and electrification. Inhibitors, fillers, and the like.
• the shape of the molded product can be appropriately selected according to the application and purpose. Examples thereof include coating film-like, film-like, sheet-like, plate-like, lens-like, tubular and fibrous shapes.
• the molded article of the present invention is preferably used for optical members.
• optical members include ultraviolet cut filters, lenses, protective materials, and the like.
• the ultraviolet cut filter can be used for articles such as optical filters, display devices, solar cells, and window glass.
• the type of display device is not particularly limited, but examples thereof include a liquid crystal display device and an organic electroluminescence display device.
• the molded article of the present invention When the molded article of the present invention is used as a lens, the molded article of the present invention itself may be formed into a lens shape and used. In addition, the molded article of the present invention may be used as a coating film on the surface of a lens, an intermediate layer of a cemented lens, or the like. Cemented lenses include those described in paragraphs 0094 to 0102 of WO2019/131572, the contents of which are incorporated herein.
• the type of protective material is not particularly limited, but includes protective materials for display devices, protective materials for solar cells, protective materials for window glass, organic electroluminescence display devices, and the like.
• the shape of the protective material is not particularly limited, but examples thereof include a coating film shape, a film shape, and a sheet shape.
• optical member of the present invention includes the molded article of the present invention described above.
• optical members include ultraviolet cut filters, lenses, protective materials, and the like.
• the ultraviolet cut filter can be used for articles such as optical filters, display devices, solar cells, and window glass.
• the type of display device is not particularly limited, but examples thereof include a liquid crystal display device and an organic electroluminescence display device.
• Examples of the lens include those obtained by forming the molded article of the present invention itself into a lens shape; and those using the molded article of the present invention as a coating film on the surface of the lens, an intermediate layer of a cemented lens, and the like.
• the type of protective material is not particularly limited, but includes protective materials for display devices, protective materials for solar cells, protective materials for window glass, and the like.
• the shape of the protective material is not particularly limited, but examples thereof include a coating film shape, a film shape, and a sheet shape.
• the optical member of the present invention can be preferably used as a constituent member of displays such as liquid crystal displays (LCDs) and organic electroluminescence displays (OLEDs).
• LCDs liquid crystal displays
• OLEDs organic electroluminescence displays
• liquid crystal display devices examples include liquid crystal display devices containing the molded article of the present invention in members such as antireflection films, polarizing plate protective films, optical films, and retardation films.
• the optical member of the present invention may be placed on either the viewer side (front side) or the backlight side with respect to the liquid crystal cell, and may be placed on the far side (outer) or near the polarizer from the liquid crystal cell. Can be placed on either side (inner).
• Examples of the organic electroluminescence display device include an organic electroluminescence display device containing the molded article of the present invention as a member such as an optical film, a protective film for a polarizing plate in a circularly polarizing plate, and a retardation film such as a quarter-wave plate. be done.
• an organic electroluminescence display device containing the molded article of the present invention as a member such as an optical film, a protective film for a polarizing plate in a circularly polarizing plate, and a retardation film such as a quarter-wave plate.
• Me is a methyl group
• Et is an ethyl group
• Bu is a butyl group
• tBu is a tert-butyl group
• Pr is a propyl group
• Ph is a phenyl group.
• Ac is an acetyl group.
• intermediate 1-3 was synthesized according to the following synthetic scheme. 90 g of Intermediate 1-1, 73.7 g of Intermediate 1-2 and 300 ml of N-methylpyrrolidone were added and mixed, followed by stirring at 60° C. for 1 hour. After cooling to room temperature, 2700 ml of water was added and stirred for 30 minutes. After filtering the precipitated solid, 300 ml of acetonitrile was added, and the mixture was heated under reflux for 1 hour in a nitrogen atmosphere. After cooling to room temperature and stirring at room temperature for 1 hour, the solid was collected by filtration and washed with 150 ml of acetonitrile to obtain 106 g of intermediate 1-3 (yield 85%).
• ⁇ Measurement of maximum absorption wavelength ( ⁇ max)> A sample solution was prepared by dissolving 2 mg of the compound shown in the table below in 100 mL of ethyl acetate and then diluting the solution with ethyl acetate so that the absorbance of the solution was in the range of 0.6 to 1.2. The absorbance of each sample solution was measured in a 1 cm quartz cell using a spectrophotometer UV-1800PC (manufactured by Shimadzu Corporation). The maximum absorption wavelength ( ⁇ max) was measured from the absorption spectrum of each sample solution.
• Polycarbonate resin manufactured by Sumika Polycarbonate Co., Ltd., SD polycarbonate 301-30, glass transition point 145 to 150 ° C.
• the transmittance of the molded plate at a wavelength of 400 nm, the transmittance at a wavelength of 410 nm, and the transmittance at a wavelength of 440 nm were measured.
• the transmittance was measured using a polycarbonate resin to which no ultraviolet absorber was added as a reference.
• Polycarbonate resin manufactured by Sumika Polycarbonate Co., Ltd., SD polycarbonate 301-30, glass transition point 145 to 150 ° C.
• the molded plates of Examples 3-1 to 3-15 had good wet heat resistance. Further, when the molded plates of Examples 3-1 to 3-15 were evaluated for light resistance in the same manner as in Test Example 2, they had excellent light resistance.
• Example 4 (Examples 4-1 to 4-4) 1 kg of polymethyl methacrylate resin (PMMA) and 0.8 g of an ultraviolet absorber listed in the table below were stirred in a stainless steel tumbler for 1 hour. This mixture was melt mixed in a vented extruder at 230 to 240° C. to prepare pellets for molding by a conventional method. After the pellets were dried at 80° C. for 3 hours, they were molded with a press to produce a molded plate with a thickness of 0.15 mm. The obtained molded plate was evaluated for light resistance in the same manner as in Test Example 2.
• PMMA polymethyl methacrylate resin
• an ultraviolet absorber listed in the table below This mixture was melt mixed in a vented extruder at 230 to 240° C. to prepare pellets for molding by a conventional method. After the pellets were dried at 80° C. for 3 hours, they were molded with a press to produce a molded plate with a thickness of 0.15 mm. The obtained molded plate was evaluated for light resistance
• Example 4-5 to 4-8 1 kg of polyethylene terephthalate (PET) pellets dried at 130° C. for 6 hours and 0.8 g of the ultraviolet absorber shown in the table below were stirred in a stainless steel tumbler for 1 hour. This mixture was melt mixed in a vented extruder at 265-280° C. to prepare pellets for molding by a conventional method. After the pellets were dried at 80° C. for 3 hours, they were molded with a press to produce a molded plate with a thickness of 0.15 mm. The obtained molded plate was evaluated for light resistance in the same manner as in Test Example 2.
• PET polyethylene terephthalate
• Examples 4-9 to 4-12 1 kg of cycloolefin polymer (COP) pellets dried at 100° C. for 6 hours and 0.8 g of the ultraviolet absorber shown in the table below were stirred in a stainless steel tumbler for 1 hour. This mixture was melt mixed in a vented extruder at 260-290° C. to prepare pellets for molding by a conventional method. After the pellets were dried at 80° C. for 3 hours, they were molded with a press to produce a molded plate with a thickness of 0.15 mm. The obtained molded plate was evaluated for light resistance in the same manner as in Test Example 2.
• COP cycloolefin polymer
• Examples 4-13 to 4-16 1 kg of nylon-66 (PA-66) pellets dried at 80° C. for 16 hours and 0.8 g of the ultraviolet absorber shown in the table below were stirred in a stainless steel tumbler for 1 hour. This mixture was melt mixed in a vented extruder at 270-290° C. to prepare pellets for molding by a conventional method. After the pellets were dried at 80° C. for 3 hours, they were molded with a press to produce a molded plate with a thickness of 0.15 mm. The obtained molded plate was evaluated for light resistance in the same manner as in Test Example 2.
• PA-66 nylon-66
• Examples 4-17 to 4-20 1 kg of polypropylene (PP) pellets and 0.8 g of an ultraviolet absorber shown in the table below were stirred in a stainless steel tumbler for 1 hour. This mixture was melt mixed in a vented extruder at 230-250° C. to prepare pellets for molding by a conventional method. After the pellets were dried at 80° C. for 3 hours, they were molded with a press to produce a molded plate with a thickness of 0.15 mm. The obtained molded plate was evaluated for light resistance in the same manner as in Test Example 2.
• PP polypropylene
• the molded plates of Examples 4-1 to 4-20 had good light resistance.
• the numerical value described in the column of light resistance in the above table is the value of the residual transmittance (%).
• the molded plates of Examples 4-1 to 4-20 were evaluated for resistance to heat and humidity in the same manner as in Test Example 1, and were found to have excellent resistance to heat and humidity.
• the kneaded products of Examples can be suitably used for each member constituting a liquid crystal display device or an organic electroluminescence display device.

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