Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
  • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
  • C07D495/04—Ortho-condensed systems
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
• • 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
  • C08K5/3447—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
  • C08K5/36—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
  • 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
  • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
• • 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
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B57/00—Other synthetic dyes of known constitution
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/006—Preparation of organic pigments
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/22—Absorbing filters
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/22—Absorbing filters
  • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/003—Light absorbing elements

Definitions

• the present invention relates to a resin composition containing an ultraviolet absorber.
• the present invention also relates to a cured product and an optical member using the resin composition.
• the present invention also relates to an ultraviolet absorber, a compound, a method for producing the compound, and a polymer.
• Patent Literature 1 describes the use of a specific benzobisdithiol as an ultraviolet absorber.
• UV absorbers One of the required characteristics of UV absorbers is that they have little coloration. Moreover, in recent years, it is required to have a high absorbability for ultraviolet light having a longer wavelength around 400 nm.
• 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 fastness, and the ultraviolet absorption ability tends to decrease over time. For this reason, in recent years, further improvement in the performance of UV absorbers in terms of light resistance has been desired.
• an object of the present invention is to provide a resin composition that has excellent ability to absorb ultraviolet light in the vicinity of a wavelength of 400 nm, is less colored, and can be used to produce a cured product having excellent light resistance.
• Another object of the present invention is to provide a cured product, an optical member, an ultraviolet absorber, a compound, a method for producing the compound, and a polymer.
• the inventor of the present invention conducted intensive studies on a compound having a skeleton represented by formula ( 1 ) .
• the present inventors have completed the present invention based on the finding that the compound has excellent ability to absorb ultraviolet rays in the vicinity, little coloration, and excellent light resistance. Accordingly, the present invention provides the following.
• a resin composition containing a compound represented by Formula (1) and a resin
• Q 1 represents a group represented by formula (Q-1);
• R 1 and R 2 each independently represent a hydrogen atom or a substituent;
• X 1 to X 4 each independently represent -S-, -NR X1 -, or -SO 2 -, and
• R X1 represents a hydrogen atom or an alkyl group;
• * represents a bond
• R 101 and R 102 each independently have a hydrogen atom, an alkyl group, an aral
• R 101 and R 102 represents a group containing a polymerizable group; provided that when one of R 101 and R 102 is a hydrogen atom, the other represents an alkyl group, an aralkyl group, an aryl group, a heterocyclic group or a group containing a polymerizable group having an ethylenically unsaturated bond, When either one of R 101 and R 102 is a methyl group, the other contains a hydrogen atom, an alkyl group having 2 or more carbon atoms, an aralkyl group, an aryl group, a heterocyclic group or a polymerizable group having an ethylenically unsaturated bond.
• R 101 and R 102 represents the group, When one of R 101 and R 102 is a phenyl group, the other is a hydrogen atom, an alkyl group, an aralkyl group, an aryl group having a substituent, a heterocyclic group, or a group containing a polymerizable group having an ethylenically unsaturated bond.
• R 101 and R 102 each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a heterocyclic group; when one of R 101 and R 102 is a hydrogen atom, the other represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group; when one of R 101 and R 102 is a methyl group, the other is a hydrogen atom, an alkyl group having 2 or more carbon atoms, an aralkyl group, an aryl group or a heterocyclic group; When either one of R 101 and R 102 is a phenyl group, the other represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group having a substituent, or a heterocyclic group.
• the resin composition according to ⁇ 1>. ⁇ 3> The resin composition according to ⁇ 1> or ⁇ 2>, wherein the compound represented by formula (1) is a compound represented by formula (3);
• Q 3 represents a group represented by formula (Q-1) above;
• R y11 represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group
• Y 11 is an alkyl group, an aralkyl group or an aryl
• the resin composition according to ⁇ 3> which represents a group.
• the resin is selected from (meth)acrylic resin, polystyrene resin, polyester resin, polyurethane resin, thiourethane resin, polyimide resin, polyamide resin, epoxy resin, polycarbonate resin, phthalate resin, cellulose acylate resin and cyclic olefin resin.
• ⁇ 7> A cured product obtained using the resin composition according to any one of ⁇ 1> to ⁇ 6>.
• Q 1 represents a group represented by formula (Q-1);
• R 1 and R 2 each independently represent a hydrogen atom or a substituent;
• X 1 to X 4 each independently represent -S-, -NR X1 -, or -SO 2 -, and
• R X1 represents a hydrogen atom
• R 101 and R 102 represents a group containing a polymerizable group; provided that when one of R 101 and R 102 is a hydrogen atom, the other represents an alkyl group, an aralkyl group, an aryl group, a heterocyclic group or a group containing a polymerizable group having an ethylenically unsaturated bond, When either one of R 101 and R 102 is a methyl group, the other contains a hydrogen atom, an alkyl group having 2 or more carbon atoms, an aralkyl group, an aryl group, a heterocyclic group or a polymerizable group having an ethylenically unsaturated bond.
• R 101 and R 102 represents the group, When one of R 101 and R 102 is a phenyl group, the other is a hydrogen atom, an alkyl group, an aralkyl group, an aryl group having a substituent, a heterocyclic group, or a group containing a polymerizable group having an ethylenically unsaturated bond.
• R 101 and R 102 each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a heterocyclic group; when one of R 101 and R 102 is a hydrogen atom, the other represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group; when one of R 101 and R 102 is a methyl group, the other is a hydrogen atom, an alkyl group having 2 or more carbon atoms, an aralkyl group, an aryl group or a heterocyclic group; When either one of R 101 and R 102 is a phenyl group, the other represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group having a substituent, or a heterocyclic group.
• Q 3 represents a group represented by formula (Q-1);
• R 101 and R 102 represents a group containing a polymerizable group; provided that when one of R 101 and R 102 is a hydrogen atom, the other represents an alkyl group, an aralkyl group, an aryl group, a heterocyclic group or a group containing a polymerizable group having an ethylenically unsaturated bond, When either one of R 101 and R 102 is a methyl group, the other contains a hydrogen atom, an alkyl group having 2 or more carbon atoms, an aralkyl group, an aryl group, a heterocyclic group or a polymerizable group having an ethylenically unsaturated bond.
• R 101 and R 102 represents the group, When one of R 101 and R 102 is a phenyl group, the other is a hydrogen atom, an alkyl group, an aralkyl group, an aryl group having a substituent, a heterocyclic group, or a group containing a polymerizable group having an ethylenically unsaturated bond.
• R y11 represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group
• Y 11 is an alkyl group
• an aralkyl group or an aryl represents the group
• R 101 and R 102 each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a heterocyclic group; when one of R 101 and R 102 is a hydrogen atom, the other represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group; when one of R 101 and R 102 is a methyl group, the other is a hydrogen atom, an alkyl
• a method for producing a compound comprising reacting a compound represented by formula (4) with a compound represented by formula (5) to produce a compound represented by formula (6);
• Q 5 represents a group represented by formula (Q-1)
• R q21 to R q23 each independently represent a hydrogen atom or a substituent, and
• R e51 represents a hydrogen atom, an alkyl
• R 101 and R 102 represents a group containing a polymerizable group; provided that when one of R 101 and R 102 is a hydrogen atom, the other represents an alkyl group, an aralkyl group, an aryl group, a heterocyclic group or a group containing a polymerizable group having an ethylenically unsaturated bond, When either one of R 101 and R 102 is a methyl group, the other contains a hydrogen atom, an alkyl group having 2 or more carbon atoms, an aralkyl group, an aryl group, a heterocyclic group or a polymerizable group having an ethylenically unsaturated bond.
• R 101 and R 102 represents the group, When one of R 101 and R 102 is a phenyl group, the other is a hydrogen atom, an alkyl group, an aralkyl group, an aryl group having a substituent, a heterocyclic group, or a group containing a polymerizable group having an ethylenically unsaturated bond.
• R 101 and R 102 each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a heterocyclic group; when one of R 101 and R 102 is a hydrogen atom, the other represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group; when one of R 101 and R 102 is a methyl group, the other is a hydrogen atom, an alkyl group having 2 or more carbon atoms, an aralkyl group, an aryl group or a heterocyclic group; When either one of R 101 and R 102 is a phenyl group, the other represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group having a substituent, or a heterocyclic group.
• ⁇ 16> A polymer containing a structure derived from the compound according to ⁇ 13>.
• the present invention it is possible to provide a resin composition that can produce a cured product that has excellent ability to absorb ultraviolet light with a wavelength of about 400 nm, is less colored, and has excellent light resistance. Moreover, the present invention can provide a cured product, an optical member, an ultraviolet absorber, a compound, a method for producing a compound, and a polymer.
• 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 resin 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 resin composition of the present invention is characterized by containing a compound represented by Formula (1) and a resin.
• the compound represented by the formula (1) is a compound that has an excellent ability to absorb ultraviolet light having a wavelength of about 400 nm, is less colored, and has excellent light resistance such that decomposition due to light irradiation is unlikely to occur. For this reason, the resin composition of the present invention can be used to produce a cured product that has excellent ability to absorb ultraviolet light having a wavelength of about 400 nm, little coloration, and excellent light resistance.
• the resin composition of the present invention may be a solution-state composition containing a solvent.
• the resin composition of the present invention may be a kneaded product.
• the kneaded product is obtained by kneading the compound represented by the formula (1) and the resin. That is, the kneaded product in this specification is a product in which the compound represented by formula (1) is mixed and dispersed in a resin, and the compound represented by formula (1) and the resin are mixed in a solvent. is different from a solution in which the is dissolved or dispersed.
• the kneaded material is also 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 pellets are preferably master pellets (masterbatch). Master pellets (masterbatch) are materials in which additives such as high-concentration UV absorbers are dispersed in resin. Used.
• the resin composition of the present invention contains a compound represented by Formula (1) (hereinafter also referred to as a specific compound).
• Q 1 represents a group represented by formula (Q-1);
• R 1 and R 2 each independently represent a hydrogen atom or a substituent;
• X 1 to X 4 each independently represent -S-, -NR X1 -, or -SO 2 -, and
• R X1 represents a hydrogen atom or an alkyl group;
• * represents a bond
• R 101 and R 102 represents a group containing a polymerizable group; provided that when either one of R 101 and R 102 is a hydrogen atom, the other represents an alkyl group, an aralkyl group, an aryl group, a heterocyclic group or a group containing a polymerizable group having an ethylenically unsaturated bond,
• R 101 and R 102 is a methyl group
• the other contains a hydrogen atom, an alkyl group having 2 or more carbon atoms, an aralkyl group, an aryl group, a heterocyclic group, or a polymerizable group having an ethylenically unsaturated bond.
• R 101 and R 102 represents the group, When one of R 101 and R 102 is a phenyl group, the other is a hydrogen atom, an alkyl group, an aralkyl group, an aryl group having a substituent, a heterocyclic group, or a group containing a polymerizable group having an ethylenically unsaturated bond.
• R y11 represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group
• Y 11 represents an alkyl group, an aralkyl group or an aryl group.
• the number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 8.
• 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 number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, still more preferably 6 to 15, particularly preferably 6 to 10, and most preferably 6 to 8.
• the aryl group may have a substituent. Examples of the substituent include the groups described for the substituent T described later.
• the number of carbon atoms in the alkyl portion of the aralkyl group is preferably 1-10, more preferably 1-5, and even more preferably 1-3.
• the number of carbon atoms in the aryl portion of the aralkyl group is preferably 6-30, more preferably 6-20, even more preferably 6-15, particularly preferably 6-10, and most preferably 6-8.
• the aralkyl group may have a substituent. Examples of the substituent include the groups described for the substituent T described later.
• a specific example of the aralkyl group includes a benzyl group.
• the heterocyclic ring in the above 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.
• 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.
• halogen atoms examples include chlorine atoms, bromine atoms, and iodine atoms.
• the polymerizable group having an ethylenically unsaturated bond in the group containing a polymerizable group having an ethylenically unsaturated bond includes a vinyl group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group. , (meth)acryloylamino group and vinylphenyl group, preferably (meth)acryloyloxy group and vinylphenyl group.
• Examples of the group containing a polymerizable group having an ethylenically unsaturated bond include groups represented by formula (T1) shown below. *-X T1 -Y T1 -Z T1 (T1)
• Rx 1 is a hydrogen atom
• Y T1 represents a single bond or a divalent linking group
• Z T1 represents a polymerizable group having an ethylenically unsaturated bond.
• 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 divalent linking group represented by YT1 includes a hydrocarbon group and a group in which two or more hydrocarbon groups are linked via a single bond or a linking group.
• 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.
• 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.
• Examples of the polymerizable group having an ethylenically unsaturated bond represented by Z T1 include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acryloylamino group, and a vinylphenyl group. , (meth)acryloyloxy and vinylphenyl groups.
• T1 Specific examples of the group represented by formula (T1) include groups represented by T-1 to T-28 below. Me in the structural formulas below is a methyl group, and * is a bond.
• -Y 11 is more preferred.
• R y11 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.
• Y 11 is preferably an alkyl group, more preferably a linear or branched alkyl group, even more preferably a branched alkyl group, because of its excellent solubility.
• Another embodiment includes an embodiment in which at least one of R 1 and R 2 is a group containing a polymerizable group having an ethylenically unsaturated bond. According to this aspect, it is possible to obtain the effect of suppressing bleeding out in the resin.
• X 1 to X 4 - X 1 to X 4 in Formula (1) each independently represent -S-, -NR X1 -, or -SO 2 -, and R X1 represents a hydrogen atom or an alkyl group.
• the preferred range of the alkyl group represented by R X1 is the same as the alkyl group described above.
• R X1 is preferably a hydrogen atom.
• X 1 to X 4 in formula (1) are preferably -S- because the effects of the present invention are exhibited more remarkably.
• R 101 and R 102 in formula (Q-1) each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, a heterocyclic group or a group containing a polymerizable group having an ethylenically unsaturated bond. .
• R 101 and R 102 when either one of R 101 and R 102 is a hydrogen atom, the other represents an alkyl group, an aralkyl group, an aryl group, a heterocyclic group or a group containing a polymerizable group having an ethylenically unsaturated bond, and R 101 or when one of R 102 is a methyl group, the other is a hydrogen atom, an alkyl group having 2 or more carbon atoms, an aralkyl group, an aryl group, a heterocyclic group, or a group containing a polymerizable group having an ethylenically unsaturated bond
• R 101 and R 102 is a phenyl group
• the other is a hydrogen atom, an alkyl group, an aralkyl group, an aryl group having a substituent, a heterocyclic group or a polymerizable group having an ethylenically unsaturated bond. represents a group containing
• the alkyl group represented by R 101 and R 102 preferably has 1 to 30 carbon atoms.
• the upper limit is preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, and even more preferably 8 or less.
• the lower limit is preferably 2 or more, more preferably 3 or more.
• 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 represented by R 101 and R 102 preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, still more preferably 6 to 15 carbon atoms, particularly preferably 6 to 10 carbon atoms, and most preferably 6 to 8 carbon atoms.
• the aryl group may have a substituent. Examples of the substituent include the groups described for the substituent T described later.
• the number of carbon atoms in the alkyl portion of the aralkyl group represented by R 101 and R 102 is preferably 1-10, more preferably 1-5, even more preferably 1-3.
• the number of carbon atoms in the aryl portion of the aralkyl group is preferably 6-30, more preferably 6-20, even more preferably 6-15, particularly preferably 6-10, and most preferably 6-8.
• the aralkyl group may have a substituent. Examples of the substituent include the groups described for the substituent T described later.
• the heterocyclic groups represented by R 101 and R 102 include the heterocyclic groups described above.
• the group containing a polymerizable group having an ethylenically unsaturated bond represented by R 101 and R 102 includes a group represented by formula (V1). *-X V1 -Y V1 -Z V1 (V1)
• Rx 2 is represents a hydrogen atom, an alkyl group or an aryl group
• Y V1 represents a single bond or a divalent linking group
• Z V1 represents a polymerizable group having an ethylenically unsaturated bond.
• the alkyl group and aryl group represented by Rx 2 are synonymous with the alkyl group and aryl group represented by Rx 1 of the group represented by formula (T1), and the preferred ranges are also the same.
• Rx 2 is preferably a hydrogen atom.
• the divalent linking group represented by YV1 includes the groups described as the divalent linking group represented by YT1 of the group represented by formula (T1), and the preferred range is also the same.
• Examples of the polymerizable group having an ethylenically unsaturated bond represented by Z V1 include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acryloylamino group, and a vinylphenyl group. , (meth)acryloyloxy and vinylphenyl groups.
• V1 Specific examples of the group represented by formula (V1) include groups represented by V-1 to V-12 below. * in the following structural formulas is a bond.
• each of R 101 and R 102 independently represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a heterocyclic group, when one of R 101 and R 102 is a hydrogen atom, the other represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group; when one of R 101 and R 102 is a methyl group, the other is a hydrogen atom, an alkyl group having 2 or more carbon atoms, an aralkyl group, an aryl group or a heterocyclic group; When one of R 101 and R 102 is a phenyl group, the other is a hydrogen atom, an alkyl group, an aralkyl group, an aryl group having a substituent, or a heterocyclic group.
• R 101 and R 102 in formula (Q-1) are each independently preferably an alkyl group or an aralkyl group, more preferably an aralkyl group.
• R 101 and R 102 are alkyl groups
• the alkyl groups represented by R 101 and R 102 are preferably independently alkyl groups having 2 or more carbon atoms.
• R 101 and R 102 in formula (Q-1) At least one of R 101 and R 102 in formula (Q-1) is a group containing a polymerizable group having an ethylenically unsaturated bond. aspects. According to this aspect, it is possible to obtain the effect of suppressing bleeding out in the resin.
• Substituents represented by R q1 to R q3 include a cyano group, a carbamoyl group, a sulfamoyl group, a nitro group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. group, an alkyl group, an aryl group, a heterocyclic group, a group containing a polymerizable group having an ethylenically unsaturated bond, and the like. These groups may further have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.
• the carbamoyl group includes a carbamoyl group having 1 to 10 carbon atoms, preferably a carbamoyl group having 2 to 8 carbon atoms, more preferably a carbamoyl group having 2 to 5 carbon atoms.
• the sulfamoyl group includes a sulfamoyl group having 0 to 10 carbon atoms, preferably a sulfamoyl group having 2 to 8 carbon atoms, and more preferably a sulfamoyl group having 2 to 5 carbon atoms.
• the acyl group includes an acyl group having 1 to 20 carbon atoms, preferably an acyl group having 1 to 12 carbon atoms, and more preferably an acyl group having 1 to 8 carbon atoms.
• the alkylsulfonyl group includes an alkylsulfonyl group having 1 to 20 carbon atoms, preferably an alkylsulfonyl group having 1 to 10 carbon atoms, more preferably an alkylsulfonyl group having 1 to 8 carbon atoms.
• the arylsulfonyl group includes an arylsulfonyl group having 6 to 20 carbon atoms, preferably an arylsulfonyl group having 6 to 10 carbon atoms.
• the alkylsulfinyl group includes an alkylsulfinyl group having 1 to 20 carbon atoms, preferably an alkylsulfinyl group having 1 to 10 carbon atoms, more preferably an alkylsulfinyl group having 1 to 8 carbon atoms.
• the arylsulfinyl group includes an arylsulfinyl group having 6 to 20 carbon atoms, preferably an arylsulfinyl group having 6 to 10 carbon atoms.
• the alkoxycarbonyl group includes an alkoxycarbonyl group having 2 to 20 carbon atoms, preferably an alkoxycarbonyl group having 2 to 12 carbon atoms, and more preferably an alkoxycarbonyl group having 2 to 8 carbon atoms.
• the aryloxycarbonyl group includes an aryloxycarbonyl group having 6 to 20 carbon atoms, preferably an aryloxycarbonyl group having 6 to 12 carbon atoms, and an aryloxycarbonyl group having 6 to 8 carbon atoms. is more preferred.
• the alkyl group includes an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms.
• the aryl group includes an aryl group having 6 to 20 carbon atoms, preferably an aryl group having 6 to 15 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms.
• 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.
• 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.
• Groups containing a polymerizable group having an ethylenically unsaturated bond include groups represented by formula (U1). *-X U1 -Y U1 -Z U1 (U1)
• Rx 3 are synonymous with the alkyl group and aryl group represented by Rx 1 of the group represented by formula (T1), and the preferred ranges are also the same.
• Rx 3 is preferably a hydrogen atom.
• the divalent linking group represented by Y U1 includes the groups described as the divalent linking group represented by Y T1 of the group represented by formula (T1), and the preferred range is also the same.
• Examples of the polymerizable group having an ethylenically unsaturated bond represented by Z U1 include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acryloylamino group, and a vinylphenyl group. , (meth)acryloyloxy and vinylphenyl groups.
• At least one of R q2 and R q3 is preferably an electron-withdrawing group, more preferably R q2 and R q3 are an electron-withdrawing group.
• At least one of R q2 and R q3 is also preferably a group containing a polymerizable group having an ethylenically unsaturated bond.
• it is also preferred that one of R q2 and R q3 is a group containing a polymerizable group having an ethylenically unsaturated bond, and the other is an electron-withdrawing group.
• Examples of the electron-withdrawing group include substituents having a Hammett's substituent constant ⁇ p value of 0.2 or more. Hammett's substituent constant ⁇ value will be described. Hammett's rule was proposed by L. et al. P. A rule of thumb put forward by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include ⁇ p and ⁇ m values, and these values can be found in many general books. For example, J. A. Dean, ⁇ Lange's Handbook of Chemistry'' 12th edition, 1979 (Mc Graw-Hill), ⁇ Kagaku no Ryori'' extra edition, No. 122, pp. 96-103, 1979 (Nankodo), Chem.
• a substituent having a Hammett's substituent constant ⁇ p value of 0.2 or more indicates an electron-withdrawing group.
• the electron-withdrawing group is preferably a group having a Hammett's substituent constant ⁇ p value of 0.25 or more, more preferably a group having a Hammett's substituent constant ⁇ p value of 0.3 or more.
• a group having a substituent constant ⁇ p value of 0.35 or more is more preferable.
• Me represents a methyl group
• Ph represents a phenyl group.
• the values in parentheses are the ⁇ p values of representative substituents obtained from
• R q2 and R q3 each independently represent a hydrogen atom, a cyano group, a carbamoyl group, a sulfamoyl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a nitro group, an alkoxycarbonyl group, An aryloxycarbonyl group or a group containing a polymerizable group having an ethylenically unsaturated bond is preferred.
• each of R q2 and R q3 is independently a hydrogen atom, a cyano group, a carbamoyl group, a sulfamoyl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a nitro group, Examples include an alkoxycarbonyl group or an aryloxycarbonyl group.
• R q2 and R q3 are preferably a cyano group, an alkoxycarbonyl group, a nitro group or an alkylsulfonyl group, and each of R q2 and R q3 is independently a cyano group or an alkoxycarbonyl group. is more preferable.
• a preferred embodiment includes an embodiment in which R q2 and R q3 are cyano groups.
• Another preferred embodiment is an embodiment in which one of R q2 and R q3 is a cyano group and the other is an alkoxycarbonyl group.
• At least one of R q2 and R q3 is preferably a group containing a polymerizable group having an ethylenically unsaturated bond.
• Each of R q2 and R q3 may be independently a group containing a polymerizable group having an ethylenically unsaturated bond, and one of R q2 and R q3 contains a polymerizable group having an ethylenically unsaturated bond. group and the other may be an electron-withdrawing group.
• Rings other than the structure represented by formula (Q-1) include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, pyrrolidine ring, tetrahydrofuran ring, tetrahydrothiophene ring, oxazoline ring, and thiazoline ring.
• At least one of R 1 , R 2 , Q 1 and Q 2 in Formula (1) preferably contains a group containing a polymerizable group having an ethylenically unsaturated bond, and R 1 , R 2 , Q 1 and More preferably, one or two of Q2 contain a group containing a polymerizable group having an ethylenically unsaturated bond.
• the number of polymerizable groups having an ethylenically unsaturated bond contained in formula (1) is preferably 1 to 2.
• the specific compound is preferably a compound represented by formula (3).
• the compound represented by formula (3) is the compound of the present invention.
• Q 3 represents a group represented by formula (Q-1) above;
• R y11 represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group
• Y 11 is an alkyl group , represents an aralkyl group or an aryl group.
• Q3 and Q4 in formula ( 3 ) are synonymous with Q1 and Q2 in formula (1), and the preferred ranges are also the same. Further, the preferred ranges of R y11 and Y 11 in formula (3) are synonymous with R y11 and Y 11 explained in formula (1).
• Another embodiment includes an embodiment in which at least one of R 11 and R 12 is a group containing a polymerizable group having an ethylenically unsaturated bond.
• At least one of R 11 , R 12 , Q 3 and Q 4 in formula (3) preferably contains a group containing a polymerizable group having an ethylenically unsaturated bond, and R 11 , R 12 , Q 3 and More preferably, one or two of Q4 contain a group containing a polymerizable group having an ethylenically unsaturated bond.
• R 11 , R 12 , R q12 , R q13 , R 101 and R 102 more preferably contain a group containing a polymerizable group having an ethylenically unsaturated bond preferable.
• the number of polymerizable groups having an ethylenically unsaturated bond contained in formula (3) is preferably 1 to 2.
• the specific compound is preferably a compound represented by formula (6).
• Q 5 represents a group represented by formula (Q-1) above
• Q5 and Q6 in formula (6) have the same meanings as Q1 and Q2 in formula (1), and the preferred ranges are also the same. Further, the preferred ranges of R y61 and Y 61 in formula (6) are synonymous with R y11 and Y 11 explained in formula (1).
• 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 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 3 to 30 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-
• 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.
• p-methoxyphenylcarbonyloxy 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
• 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
• 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; for example, 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 dioctyloxy
• 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.
• Specific examples of the specific compound include compounds having the following structures.
• Et is an ethyl group
• Me is a methyl group
• n Bu is a normal butyl group
• t Bu is a tert-butyl group
• Ph is a phenyl group.
• a specific compound is preferably used as an ultraviolet absorber.
• the maximum absorption wavelength of the specific compound preferably exists in the wavelength range of 380-420 nm, more preferably in the wavelength range of 390-410 nm.
• the specific compound preferably has a ratio of absorbance at a wavelength of 440 nm to 1 at a wavelength of 400 nm of less than 0.02.
• the molar extinction coefficient of the specific compound at the maximum absorption wavelength is preferably 80000 L/mol ⁇ cm or more, more preferably 85000 L/mol ⁇ cm or more, and even more preferably 90000 L/mol ⁇ cm or more.
• the molar extinction coefficient at a wavelength of 400 nm is preferably 30000 L/mol ⁇ cm or more, more preferably 40000 L/mol ⁇ cm or more, and even more preferably 50000 L/mol ⁇ cm or more.
• the molar absorption coefficient at a wavelength of 440 nm is preferably 1000 L/mol ⁇ cm or less, more preferably 800 L/mol ⁇ cm or less, and even more preferably 600 L/mol ⁇ cm or less.
• the absorbance, maximum absorption wavelength and molar extinction coefficient of a specific compound are obtained 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). can be done. Examples of measuring devices include a spectrophotometer (UV-1800PC, manufactured by Shimadzu Corporation).
• the specific compound can be produced according to the method described in International Publication No. 2009/022736.
• the compound represented by formula (6) can also be produced by reacting the compound represented by formula (4) with the compound represented by formula (5).
• Q 5 represents a group represented by formula (Q-1) above
• R e51 represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group
• Re52 represents -Cl or an alkoxy group
• Y51 represents an alkyl group, an aralkyl group or an aryl group.
• Q5 and Q6 in formula (4) are synonymous with Q5 and Q6 in formula (6), and the preferred ranges are also the same.
• the number of carbon atoms in the alkyl group represented by Y 51 in formula (5) is preferably 1 to 30, more preferably 1 to 20, even more preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 8.
• 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 above.
• the number of carbon atoms in the aryl group represented by Y 51 in formula (5) is preferably 6-30, more preferably 6-20, still more preferably 6-15, particularly preferably 6-10, and most preferably 6-8.
• the aryl group may have a substituent. Examples of the substituent include the groups described for the substituent T described above.
• the number of carbon atoms in the alkyl portion of the aralkyl group represented by Y 51 in formula (5) is preferably 1-10, more preferably 1-5, and even more preferably 1-3.
• the number of carbon atoms in the aryl portion of the aralkyl group is preferably 6-30, more preferably 6-20, still more preferably 6-15, particularly preferably 6-10, and most preferably 6-8.
• the aralkyl group may have a substituent. Examples of the substituent include the groups described for the substituent T described above.
• Y 51 in formula (5) is preferably an alkyl group.
• the alkyl group, aralkyl group and aryl group represented by R e51 in E 51 of formula (5) are the same as the groups described for Y 51 of formula (5).
• the number of carbon atoms in the alkoxy group represented by R e52 in E 51 of formula (5) is preferably from 1 to 30, more preferably from 1 to 20, still more preferably from 1 to 15, particularly preferably from 1 to 10, and from 1 to 8. Most preferred.
• the reaction between the compound represented by formula (4) and the compound represented by formula (5) can be carried out in an organic solvent.
• the organic solvent is not particularly limited, but for example, dimethylformamide, dimethylacetamide, amide solvents such as N-methyl-2-pyrrolidone, tetrahydrofuran, acetonitrile, toluene, methanol, ethanol, isopropyl alcohol, and mixtures thereof. is preferred, and dimethylformamide or dimethylacetamide is particularly preferred.
• the reaction ratio between the compound represented by formula (4) and the compound represented by formula (5) can be appropriately set according to the desired structure of the compound represented by formula (6).
• the reaction temperature is not particularly limited, it is preferably from 0° C. to the boiling point of the reaction solvent.
• the reaction time is not particularly limited, but can be, for example, 1 hour to 48 hours.
• the content of the specific compound in the total solid content of the resin composition is preferably 0.01 to 50% by mass.
• the lower limit is preferably 0.05% by mass or more, more preferably 0.1% by mass or more.
• the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less.
• the content of the specific compound is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the resin.
• the lower limit is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more.
• the upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less.
• the resin composition 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.
• the resin composition of the present invention contains a resin.
• the resin can be appropriately selected from resins satisfying physical properties such as transparency, refractive index, workability, etc. required according to the application or purpose.
• 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 resins, polyamide resins, Polyimine resin, polyurea resin, polyphosphazene resin, polysilane resin, polysilazane resin, polyfuran resin, polybenzoxazole resin, polyoxadiazole resin, polybenzothiazin
• (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 groups, ethyl groups, or phenyl groups, etc.), aliphatic dicarboxylic acids having 2 to 20 carbon atoms (e.g., adipic acid, sebacic acid, and dodecane dicarboxylic acid), or an alicyclic dicarboxylic acid (e.g., cyclohexanedicarboxylic acid, etc.)), a polymer obtained by the reaction, and a polymer obtained by ring-opening polymerization of a cyclic ester compound such
• 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 novolac 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 hydroxyl, alkoxy and carboxyl groups in 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 can be mentioned.
• 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., SMA2000P (styrene-maleic acid copolymer) manufactured by Kawase Chemical Co., Ltd., and Denka Corporation.
• Clearen 530L Clearen 730L from Asahi Kasei Corporation, Tufprene 126S, Asaprene T411 from Asahi Kasei Corporation, Kraton D1102A from Clayton Polymer Japan, Clayton D1116A from Styrolution, Stylolux S, Styrolux T from Asahi Kasei Co., Ltd.
• Commercially available hydrogenated polystyrene resins include Tuftec H series manufactured by Asahi Kasei Corporation, Kraton G series manufactured by Shell Japan, Dynalon (hydrogenated styrene-butadiene random copolymer) manufactured by JSR Corporation, Septon manufactured by Kuraray Co., Ltd., and the like can be mentioned.
• modified polystyrene resins include Tuftec M series manufactured by Asahi Kasei Corporation, Epofriend manufactured by Daicel Corporation, polar group-modified Dynalon manufactured by JSR Corporation, and Reseda manufactured by Toagosei Co., Ltd. etc.
• (R1) a polymer containing a structural unit derived from a norbornene compound
• (R2) a polymer containing a structural unit derived from a monocyclic cyclic olefin compound other than a norbornene compound
• (R3) a cyclic conjugated A polymer containing a structural unit derived from a diene compound
• (R4) a polymer containing a structural unit derived from a vinyl alicyclic hydrocarbon compound, and a structural unit derived from each of the compounds (R1) to (R4) 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.
• the cyclic olefin resin is preferably a polymer having a structural unit derived from a norbornene compound represented by formula (A-II) or formula (A-III).
• a polymer having a structural unit represented by formula (A-II) is an addition polymer of a norbornene compound
• a polymer having a structural unit represented by formula (A-III) is a ring-opening polymer of a norbornene compound. is.
• R 3 to R 6 in formulas (A-II) and (A-III) each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
• Hydrocarbon groups represented by R 3 to R 6 include alkyl groups, alkenyl groups, alkynyl groups and aryl groups, with alkyl groups and aryl groups being preferred.
• X 2 and X 3 , Y 2 and Y 3 are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom, - (CH 2 ) n COOR 11 , —(CH 2 ) n OCOR 12 , —(CH 2 ) n NCO, —(CH 2 ) n NO 2 , —(CH 2 ) n CN, —(CH 2 ) n CONR 13 R 14 , —(CH 2 ) n NR 13 R 14 , —(CH 2 ) n OZ 1 , —(CH 2 ) n W 1 , or X 2 and Y 2 or X 3 and Y 3 are bonded to each other represents (—CO) 2 O or (—CO) 2 NR 15 to form.
• R 11 to R 15 in the above groups that can be taken as X 2 , X 3 , Y 2 and Y 3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
• Z 1 is represents a hydrocarbon group or a halogen-substituted hydrocarbon group
• W 1 is Si(R 16 ) p D (3-p)
• R 16 represents a hydrocarbon group having 1 to 10 carbon atoms
• D is a halogen atom
• —OCOR 17 or —OR 17 R 17 is a hydrocarbon group having 1 to 10 carbon atoms
• p is an integer of 0 to 3
• n is an integer of 0 to 10, preferably 0 to 8, more preferably 0 to 6.
• R 3 to R 6 in formulas (A-II) and (A-III) are each independently preferably a hydrogen atom or —CH 3 , more preferably a hydrogen atom in terms of moisture permeability.
• X 2 and X 3 are each preferably a hydrogen atom, -CH 3 or -C 2 H 5 , more preferably a hydrogen atom from the viewpoint of moisture permeability.
• Y 2 and Y 3 are each independently preferably a hydrogen atom, a halogen atom (especially a chlorine atom) or —(CH 2 ) n COOR 11 (especially —COOCH 3 ), more preferably a hydrogen atom in terms of moisture permeability. .
• Other groups are appropriately selected.
• a polymer having a structural unit represented by formula (A-II) or formula (A-III) may further contain one or more structural units represented by formula (AI).
• R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
• X 1 and Y 1 each independently represent a hydrogen atom, a carbon number 1 to 10 hydrocarbon group, halogen atom, halogen-substituted hydrocarbon group having 1 to 10 carbon atoms, —(CH 2 ) n COOR 11 , —(CH 2 ) n OCOR 12 , —(CH 2 ) n NCO, —(CH 2 ) n NO 2 , —(CH 2 ) n CN, —(CH 2 ) n CONR 13 R 14 , —(CH 2 ) n NR 13 R 14 , —(CH 2 ) n OZ 1 , —(CH 2 ) n W 1 , or (—CO) 2 O or (—CO) 2 NR 15 formed by combining X 2 and Y 2 or X 3 and Y 3 with each other.
• R 11 to R 15 in the above groups that can be taken as X 1 and Y 1 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and Z 1 is a hydrocarbon group or substituted with halogen represents a hydrocarbon group
• W 1 represents Si(R 16 ) p D (3-p) (R 16 represents a hydrocarbon group having 1 to 10 carbon atoms, D represents a halogen atom, -OCOR 17 or -OR 17 ( R 17 represents a hydrocarbon group having 1 to 10 carbon atoms, p represents an integer of 0 to 3).
• n represents an integer of 0-10.
• the content of the structural unit represented by formula (A-II) or formula (A-III) in the cyclic polyolefin resin is preferably 90% by mass or less, more preferably 30 to 85% by mass. It is preferably from 50 to 79% by mass, and even more preferably from 60 to 75% by mass.
• Cyclic olefin resins are described in JP-A-10-007732, JP-A-2002-504184, International Publication No. 2004/070463, etc., and the contents thereof can be referred to as appropriate.
• Cyclic olefin resins are obtained by addition polymerization of norbornene compounds (for example, polycyclic unsaturated compounds of norbornene).
• cyclic olefin resins include ARTON series manufactured by JSR Corporation (for example, ARTON G, F, RX4500), Zeonor ZF14 and ZF16 manufactured by Nippon Zeon Co., Ltd., and Zeonex 250 and 280. etc.
• cyclic olefin resins norbornene compounds, olefins such as ethylene, propylene and butene, conjugated dienes such as butadiene and isoprene, non-conjugated dienes such as ethylidenenorbornene, acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, Copolymers obtained by addition copolymerization with ethylenically unsaturated compounds such as acrylic acid esters, methacrylic acid esters, maleimide, vinyl acetate, and vinyl chloride can be mentioned. Among them, copolymers with ethylene are preferred.
• Such addition (co)polymers of norbornene compounds are sold by Mitsui Chemicals under the trade name of APEL, and have different glass transition temperatures (Tg). °C), APL6013T (Tg 125°C), or APL6015T (Tg 145°C).
• pellets such as TOPAS 8007, 6013 and 6015 are commercially available from Polyplastics.
• Appear 3000 is commercially available from Ferrania.
• hydrides of cyclic olefin resins can be synthesized by addition polymerization or ring-opening metathesis polymerization of norbornene compounds 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 2004-309979, etc.
• the weight molecular weight of the cyclic olefin resin is preferably 5,000 to 500,000, more preferably 8,000 to 200,000, and even more preferably 10,000 to 100,000.
• Polycarbonate resins include reaction products of polyhydric phenol compounds and phosgene or carbonate ester compounds.
• polyhydric phenol compounds 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 ester compounds include phosgene, diphenyl carbonate, bis(chlorophenyl) carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like. Carbonate is preferred.
• polycarbonate resins include Panlite L-1250WP and Panlite SP-1516 manufactured by Teijin Limited, Iupizeta EP-5000 and Iupizeta EP-4000 manufactured by Mitsubishi Gas Chemical Co., Ltd., and Sumika Polycarbonate Co., Ltd. caliber 301-30 manufactured by the company.
• 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 resin may have an acid group.
• 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.
• a resin having an acid group can be used as an alkali-soluble resin, and can also be used as a dispersant.
• JP 2012-208494 paragraph numbers 0558 to 0571 (corresponding US Patent Application Publication No. 2012/0235099, paragraph numbers 0685 to 0700), and JP 2012- Reference can be made to paragraphs 0076 to 0099 of Japanese Patent No. 198408, and the contents thereof are incorporated herein.
• Acrybase FF-426 manufactured by Nippon Shokubai Co., Ltd.
• the acid value of the resin having acid groups 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 resin may have a curable group.
• curable groups include ethylenically unsaturated bond-containing groups, epoxy groups, methylol groups, and alkoxysilyl groups.
• ethylenically unsaturated bond-containing groups include vinyl groups, styrene groups, allyl groups, methallyl groups, and (meth)acryloyl groups.
• Alkoxysilyl groups include, for example, monoalkoxysilyl groups, dialkoxysilyl groups, and trialkoxysilyl groups.
• resins containing a curable group include Dianal BR series (polymethyl methacrylate (PMMA), such as Dianal BR-80, BR-83, and BR-87; manufactured by Mitsubishi Chemical Corporation), Photomer 6173 (COOH-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 (eg, ACA230AA), Plaxel CF200 series (both manufactured by Daicel Corporation), Ebecryl3800 (manufactured by Daicel UCB Co., Ltd.), Acrycure-RD-F8 (manufactured by Nippon Shokubai Co., Ltd.), and the like. Further, for example, commercially available products such as the products described with the epoxy resins described above are also included.
• PMMA polymethyl methacrylate
• PMMA polymethyl methacrylate
• Photomer 6173 COOH-containing
• the resin composition of the present invention is used for a lens (for example, a spectacle lens)
• the resin is preferably a thermoplastic resin such as carbonate resin, (meth)acrylic resin, or a thermosetting resin such as urethane resin. be.
• Adhesives and adhesives can also be used for the resin.
• adhesives include acrylic adhesives, rubber adhesives, silicone adhesives, and the like.
• An acrylic pressure-sensitive adhesive is a pressure-sensitive adhesive containing a polymer of (meth)acrylic monomers ((meth)acrylic polymer).
• adhesives include urethane resin adhesives, polyester adhesives, acrylic resin adhesives, ethylene vinyl acetate resin adhesives, polyvinyl alcohol adhesives, polyamide adhesives, and silicone adhesives. Among them, a urethane resin adhesive or a silicone adhesive is preferable as the adhesive because of its high adhesive strength.
• the adhesive a commercially available product may be used.
• Examples of commercially available products include a urethane resin adhesive (LIS-073-50U: trade name) manufactured by Toyo Ink Co., Ltd., and an acrylic resin manufactured by Soken Chemical Co., Ltd. system adhesive (SK Dyne-SF2147: trade name) and the like.
• the resin is at least one selected from (meth)acrylic resins, polystyrene resins, polyester resins, polyurethane resins, thiourethane resins, polyimide resins, polyamide resins, epoxy resins, polycarbonate resins, phthalate resins, cellulose acylate resins and cyclic olefin resins.
• (Meth)acrylic resins, polystyrene resins, polyester resins, polyurethane resins, and cyclic olefins for the reason that it is preferable to be a species, has good compatibility with specific compounds, and is easy to obtain a cured product with suppressed surface unevenness. More preferably, it is at least one selected from resins.
• the weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000.
• the lower limit of Mw of the resin is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 50,000 or more.
• the upper limit of Mw of the resin 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 (Mw) of the epoxy resin is preferably 100 or more, more preferably 200 to 2,000,000.
• the upper limit of Mw of the epoxy resin is preferably 1,000,000 or less, more preferably 500,000 or less.
• the lower limit of Mw of the epoxy resin is preferably 2000 or more.
• the weight average molecular weight (Mw) 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 amount 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 total light transmittance of the resin is preferably 80% or higher, more preferably 85% or higher, even more preferably 90% or higher.
• the total light transmittance of the resin is a value measured based on the content described in "4th Edition Experimental Chemistry Course 29 Polymer Material Medium” (Maruzen, 1992) edited by The Chemical Society of Japan, pp. 225-232. is.
• the resin content in the total solid content of the resin composition is preferably 1 to 99.9% by mass.
• the lower limit is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more.
• the upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less.
• the resin composition may contain only one kind of resin, or may contain two or more kinds. When two or more resins are included, the total amount thereof is preferably within the above range.
• the resin composition of the present invention can contain an ultraviolet absorber (hereinafter also referred to as another ultraviolet absorber) other than the specific compound described above. According to this aspect, it is possible to form a cured product that can block light of wavelengths in the ultraviolet region over a wide range.
• an ultraviolet absorber hereinafter also referred to as another ultraviolet absorber
• the maximum absorption wavelength of other ultraviolet absorbers preferably exists in the wavelength range of 300 to 380 nm, more preferably in the wavelength range of 300 to 370 nm, and more preferably in the wavelength range of 310 to 360 nm. , in the wavelength range of 310 to 350 nm.
• the other ultraviolet absorber is also preferably a compound having a polymerizable group.
• polymerizable groups include vinyl groups, allyl groups, (meth)acryloyl groups, (meth)acryloyloxy groups, (meth)acryloylamino groups, and vinylphenyl groups.
• ultraviolet absorbers include aminobutadiene-based ultraviolet absorbers, dibenzoylmethane-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, acrylate-based ultraviolet absorbers, and triazine-based ultraviolet absorbers.
• examples include ultraviolet absorbers, and benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers and triazine-based ultraviolet absorbers are preferred, and benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers are more preferred.
• Specific examples of other ultraviolet absorbers include the compounds described in the examples below.
• the content of the other UV absorbers in the total solid content of the resin composition is preferably 0.01 to 50% by mass.
• the lower limit is preferably 0.05% by mass or more, more preferably 0.1% by mass or more.
• the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less. Further, the total content of the specific compound and other ultraviolet absorbers in the total solid content of the resin composition is preferably 0.01 to 50% by mass.
• the lower limit is preferably 0.05% by mass or more, more preferably 0.1% by mass or more.
• the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, and more preferably 20% by mass or less.
• the resin composition may contain only one other UV absorber, or may contain two or more. When two or more other UV absorbers are included, the total amount thereof is preferably within the above range.
• the resin composition of the present invention can contain a polymerizable compound.
• a polymerizable compound any compound that can be polymerized and cured by applying energy can be used without limitation.
• the polymerizable compound may be a radical polymerizable compound or a cationically polymerizable compound.
• the radically polymerizable compound include compounds having an ethylenically unsaturated bond-containing group.
• the polymerizable compound 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 compound 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.
• Polymerizable compounds are monomers, prepolymers (i.e., dimers, trimers, or oligomers), mixtures thereof, and (co)polymers of compounds selected from monomers and prepolymers. Although it may be present, it is preferably a monomer.
• the molecular weight of the polymerizable compound is preferably 100-3000.
• the upper limit is preferably 2000 or less, more preferably 1500 or less.
• the lower limit is preferably 150 or more, more preferably 250 or more.
• Radically polymerizable compounds examples include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters of unsaturated carboxylic acids, and amides of unsaturated carboxylic acids, and , unsaturated carboxylic acids or their esters or amides (co)polymers.
• unsaturated carboxylic acids e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
• esters of unsaturated carboxylic acids e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
• esters of unsaturated carboxylic acids e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, male
• Radically polymerizable compounds include unsaturated carboxylic acid esters or unsaturated carboxylic acid amides having nucleophilic substituents (e.g., hydroxy group, amino group, mercapto group, etc.), and monofunctional or polyfunctional isocyanate compounds or epoxy compounds.
• a compound, an addition reaction product; a dehydration condensation reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a nucleophilic substituent and a monofunctional or polyfunctional carboxylic acid; an electrophilic substituent ( addition reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having an isocyanate group, an epoxy group, etc., and a monofunctional or polyfunctional alcohol, amine or thiol; a substituted reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a halogen group, a tosyloxy group, etc., and a monofunctional or polyfunctional alcohol, amine or thiol; and the like can also be used.
• a compound obtained by replacing the above unsaturated carboxylic acid with unsaturated phosphonic acid, styrene, vinyl ether, or the like can also be used.
• a plurality of compounds with different functional numbers or a plurality of compounds with different types of polymerizable groups may be used in combination with the radically polymerizable compound.
• the radically polymerizable compound is preferably a (meth)acrylate compound, more preferably a bifunctional or higher (meth)acrylate compound, more preferably a 2- to 15-functional (meth)acrylate compound, Di- to 10-functional (meth)acrylate compounds are more preferred, and bi- to hexa-functional (meth)acrylate compounds are particularly preferred.
• radically polymerizable compounds include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri((meth)acryloyl oxyethyl) 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.
• pentaerythritol tri(meth)acrylate pentaerythritol tetra(meth)acrylate
• pentaerythritol tetra(meth)acrylate pentaerythritol tri(meth)acrylate
• radically polymerizable compounds include KAYARAD series from Nippon Kayaku Co., Ltd. (e.g., D-330, D-320, D-310, PET-30, TPA-330, DPHA, etc.), Shin-Nakamura Chemical Industry. Co., Ltd. NK ester series (e.g., A-DPH-12E, A-TMMT, A-TMM-3, etc.), Kyoeisha Chemical Co., Ltd. light acrylate series (e.g., DCP-A, etc.), Toagosei Co., Ltd.
• KAYARAD series from Nippon Kayaku Co., Ltd.
• D-330, D-320, D-310, PET-30, TPA-330, DPHA, etc. Shin-Nakamura Chemical Industry. Co., Ltd.
• NK ester series e.g., A-DPH-12E, A-TMMT, A-TMM-3, etc.
• Aronix series e.g., M-305, M-306, M-309, M-450, M-402, TO-1382, etc.
• Viscoat series e.g., V#802, etc.
• Radical polymerizable compounds include (meth)acrylate compounds described in JP-A-48-064183, JP-B-49-043191, and JP-B-52-030490, and the Japan Adhesion Society Journal vol. 20, No. 7, 300-308 (1984) as photocurable monomers and oligomers can be used.
• cationic polymerizable compounds include compounds having a cationic polymerizable group.
• cationic polymerizable groups include cyclic ether groups such as epoxy groups and oxetanyl groups, and vinyl ether groups, with cyclic ether groups being preferred.
• the cationically polymerizable compound is preferably a polyfunctional cationically polymerizable compound having two or more cationically polymerizable groups.
• Examples of cationic polymerizable compounds include polyfunctional alicyclic epoxy compounds, polyfunctional heterocyclic epoxy compounds, polyfunctional oxetane compounds, alkylene glycol diglycidyl ether, and alkylene glycol monovinyl monoglycidyl ether.
• cationic polymerizable compounds include 3′,4′-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl- 3′,4′-epoxycyclohexanecarboxylate, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, xylylene bisoxetane, 3-ethyl -3-hydroxymethyloxetane, 3-ethyl-3- ⁇ [(3-ethyloxetan-3-yl)methoxy]methyl ⁇ oxetane, cyclohexanedimethanol divinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, 4-
• a (meth)acrylate compound having a cationic polymerizable group can also be used as the cationic polymerizable compound.
• Specific examples of (meth)acrylate compounds having a cationic polymerizable group include 3,4-epoxycyclohexylmethyl methacrylate and the like. Examples of commercially available products include CYCLOMER M100 manufactured by DAICEL CORPORATION.
• the cationically polymerizable compounds include Aron oxetane series (OXT-101, OXT-121, OXT-221, etc.) manufactured by Toagosei Co., Ltd., Celoxide series (2021P) manufactured by Daicel Corporation, Nippon Carbide Industry Co., Ltd. Alkyldivinylether CHDVE, Alkylmonovinylether EHVE, Hydroxyalkylvinylether CHMVE, Hydroxyalkylvinylether HBVE, etc., manufactured by Ajinomoto Co., Inc. can also be used. Further, those exemplified as specific examples of the epoxy resin to be described later can also be used.
• the content of the polymerizable compound in the total solid content of the resin composition is preferably 0.1 to 90% by mass.
• the lower limit is preferably 1% by mass or more, more preferably 5% by mass or more.
• the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less.
• the resin composition may contain only one type of polymerizable compound, or may contain two or more types. When two or more polymerizable compounds are included, the total amount thereof is preferably within the above range.
• the resin composition 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.
• Polymerization initiators include radical polymerization initiators and cationic polymerization initiators.
• the polymerization initiator is preferably a radical polymerization initiator.
• the polymerization initiator is preferably a cationic polymerization initiator.
• the polymerization initiator can be appropriately selected from, for example, photopolymerization initiators and thermal polymerization initiators, and photopolymerization initiators are preferred.
• a photopolymerization initiator is a compound that is sensitized by exposure light and initiates or accelerates the polymerization of a polymerizable compound.
• the photopolymerization initiator includes photoradical polymerization initiators and photocationic polymerization initiators, and is preferably a photoradical polymerization initiator.
• the radical photopolymerization initiator is preferably a compound that generates radicals in response to actinic rays having a wavelength of 300 nm or longer.
• photoradical polymerization initiators include oxime compounds, halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, and acridine. compounds, organic peroxides, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, onium salt compounds, acetophenone compounds, acylphosphine compounds and benzophenone compounds. be done.
• Acetophenone compounds include aminoacetophenone compounds and hydroxyacetophenone compounds. Examples of the acetophenone compound include those described in JP-A-2009-191179 and JP-A-10-291969. Commercially available aminoacetophenone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (manufactured by IGM Resins B.V.). Commercially available hydroxyacetophenone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (manufactured by IGM Resins B.V.).
• Acylphosphine compounds include acylphosphine compounds described in Japanese Patent No. 4225898.
• Commercially available acylphosphine compounds include Omnirad 819 and Omnirad TPO (manufactured by IGM Resins B.V.).
• Benzophenone compounds include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxy carbonylbenzophenone, benzophenonetetracarboxylic acid or its tetramethyl ester, 4,4'-bis(dialkylamino)benzophenones (e.g., 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(dicyclohexylamino) Benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dihydroxyethylamino)benzophenone), 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylamino Examples
• 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 paragraphs of JP-A-2016-006475. Compounds described in Nos. 0073 to 0075 and the like can be mentioned.
• 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).
• Hexaarylbiimidazole compounds include compounds described in JP-B-06-029285, US Pat. No. 3,479,185, US Pat. No. 4,311,783, and US Pat. Specifically, 2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(o-bromophenyl))4,4′, 5,5'-Tetraphenylbiimidazole, 2,2'-bis(o,p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl) -4,4',5,5'-tetra(m-methoxyphenyl)biimidazole, 2,2'-bis(o,o'-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole
• the photocationic polymerization initiator is not particularly limited as long as it is a compound that generates protonic acid or Lewis acid upon exposure to light.
• the photoacid generator is preferably a compound that responds to actinic rays with a wavelength of 300 nm or more, more preferably 300 to 450 nm, and generates an acid.
• the photoacid generator is preferably a compound that generates an acid with a pKa of 4 or less by light irradiation, more preferably a compound that generates an acid with a pKa of 3 or less, and generates an acid with a pKa of 2 or less. It is more preferable that it is a compound that
• photocationic polymerization initiators include oxime sulfonate compounds, triazine compounds, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, iminosulfonic acid ester compounds, carboxylic acid ester compounds and sulfones. imide compounds.
• photocationic polymerization initiator paragraph numbers 0061 to 0108 of JP-A-2012-046577, compounds described in paragraph numbers 0029-0030 of JP-A-2002-122994, JP-A-2002-122994 Compounds described in paragraph numbers 0037 to 0063, oxime sulfonate compounds described in paragraph numbers 0081 to 0108 of JP-A-2013-210616, and the like.
• photocationic polymerization initiators include WPAG-469 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), CPI-100P (manufactured by San-Apro Co., Ltd.), CPI-210S (manufactured by San-Apro Co., Ltd.), Irgacure290 ( BASF Japan Ltd.) and the like.
• the thermal polymerization initiator is not particularly limited, and known thermal polymerization initiators can be used.
• thermal polymerization initiators can be used.
• the content of the polymerization initiator in the total solid content of the resin composition is preferably 0.1 to 20% by mass.
• the lower limit is preferably 0.3% by mass or more, more preferably 0.4% by mass or more.
• the upper limit is preferably 15% by mass or less, more preferably 10% by mass or less.
• the resin composition 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.
• the resin composition of the present invention can contain a catalyst.
• the catalyst include acid catalysts such as hydrochloric acid, sulfuric acid, acetic acid and propionic acid, and basic catalysts such as sodium hydroxide, potassium hydroxide and triethylamine.
• the content of the catalyst is preferably 0.1 to 100 parts by mass, more preferably 0.1 to 50 parts by mass, and still more preferably 0 parts by mass with respect to 100 parts by mass of the resin. .1 to 20 parts by mass.
• the resin composition may contain only one type of catalyst, or may contain two or more types. When two or more kinds of catalysts are included, it is preferable that the total amount thereof is 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.
• the silane coupling agent is preferably a compound having an alkoxysilyl group.
• 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.
• 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 total solid content of the resin composition 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 number of silane coupling agents may be one, or two or more. When two or more kinds are used, the total amount is preferably within the above range.
• the resin composition 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 in 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 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, 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.), F-4440
• 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 total solid content of the resin composition is preferably 0.01 to 3.0% by mass, more preferably 0.05 to 1.0% by mass, and 0.10 to 0.80% by mass. % is more preferred. Only one type of surfactant may be used, or two or more types may be used. When two or more kinds are used, the total amount is preferably within the above range.
• the resin composition preferably further contains a solvent.
• the solvent is not particularly limited, and includes water and organic solvents.
• the solvent is preferably an organic solvent.
• organic solvents examples include alcohol-based solvents, ester-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, hydrocarbon-based solvents, and halogen-based solvents.
• alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol, propylene glycol, glycerin and the like.
• ester solvents include methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and lactic acid.
• alkoxyacetic acid alkyl esters e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (specifically, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)
• 3-oxypropionic acid alkyl esters 2-oxypropionic acid alkyl esters, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl pyruvate, pyruvic acid Ethyl, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glyco
• ether solvents include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, polyethylene glycol monoalkyl ether, and polypropylene.
• amide solvents include N-methylpyrrolidone, dimethylformamide, dimethylacetamide and the like.
• ketone solvents include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone and 3-heptanone.
• hydrocarbon solvents include toluene and xylene.
• halogen solvents include chloroform and methylene chloride. These organic solvents may be used in combination of two or more.
• Organic solvents include methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethylcarbylate. It preferably contains at least one selected from tall acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.
• the solvent content in the resin composition is preferably 10 to 90% by mass, more preferably 30 to 90% by mass, even more preferably 50 to 90% by mass.
• the resin composition may contain only one type of solvent, or may contain two or more types. When two or more solvents are included, the total amount thereof is preferably within the above range. Further, when the resin composition of the present invention is used as a kneaded product, the content of the organic solvent in the resin composition is preferably 0.1% by mass or less, and is 0.01% by mass or less. is more preferred.
• the resin composition of the present invention may contain a plasticizer.
• 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.
• 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 resin composition 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 kneaded product may contain only one kind of plasticizer, or may contain two or more kinds. When two or more plasticizers are included, the total amount thereof is preferably within the above range.
• the resin composition may optionally contain optional additives such as antioxidants, light stabilizers, processing stabilizers, anti-aging agents, and compatibilizers.
• optional additives such as antioxidants, light stabilizers, processing stabilizers, anti-aging agents, and compatibilizers.
• Various properties of the obtained cured product can be appropriately adjusted by appropriately containing these components.
• the resin composition 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.; interior and exterior materials and paints for residences, facilities, transportation equipment, etc.; light source members that emit ultraviolet rays, such as fluorescent lamps and mercury lamps.
• the resin composition of the present invention can be preferably used for optical members and the like.
• it is preferably used as a resin composition 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 resin composition of the present invention can also be used as a pressure-sensitive adhesive, an adhesive, or the like.
• the resin composition 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.
• an organic electroluminescence display an optical film, a polarizing plate protective film in a circularly polarizing plate, a retardation film such as a quarter-wave plate, an adhesive or an adhesive, etc. constitute an organic electroluminescence display. It can be used for each member to be used.
• the ultraviolet absorber of the present invention contains the compound (specific compound) represented by formula (1) described above.
• the compound represented by formula (1) is the same as described above.
• Ultraviolet absorbers can also be suitably used in applications where exposure to sunlight or light containing ultraviolet light is likely. Specific examples of these include those described above.
• the ultraviolet absorber of the present invention can also be used for packaging materials, containers, paints, coatings, inks, fibers, building materials, recording media, image display devices, solar cell covers, glass coatings, and the like. Moreover, it can also be used for an optical member to be described later.
• the cured product of the present invention is obtained using the resin composition of the present invention described above.
• the term "cured product” as used herein includes a cured product obtained by drying and solidifying a resin composition, and a cured product obtained by curing a resin composition when the resin composition undergoes a curing reaction. .
• the cured product of the present invention may be obtained as a molded product obtained by molding the resin composition into a desired shape.
• the shape of the molded article 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 cured product of the present invention is preferably used as an optical member.
• optical members include ultraviolet cut filters, lenses, protective materials, and the like. It can also be used for polarizing plates 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 cured product of the present invention When using the cured product of the present invention for a lens, the cured product itself may be formed into a lens shape and used.
• the cured product of the present invention may also be used for coating films on lens surfaces, intermediate layers (adhesive layers) of cemented lenses, and 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.
• the optical member of the present invention includes a cured product obtained using the resin composition of the present invention described above.
• the cured product of the present invention may be obtained as a molded product obtained by molding the resin composition of the present invention described above into a desired shape.
• 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.
• Types of optical components include UV cut filters, lenses, and protective materials.
• 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 cured product of the present invention itself into a lens shape; and those using the cured product of the present invention as a coating film on the surface of the lens, an intermediate layer (adhesive layer or adhesive layer) of a cemented lens, and the like. be done.
• 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.
• one form of the optical member is a resin film.
• the resin film can be formed using the resin composition of the present invention described above.
• the resin used in the resin composition for forming the resin film includes the resins described above, preferably (meth)acrylic resin, polyester fiber, cyclic olefin resin and cellulose acylate resin, more preferably cellulose acylate resin.
• a resin composition containing a cellulose acylate resin may contain additives described in paragraphs 0022 to 0067 of JP-A-2012-215689. Examples of such additives include sugar esters.
• a resin film (cellulose acylate film) can be produced using a resin composition containing a cellulose acylate resin by the method described in paragraphs 0068 to 0096 of JP-A-2012-215689. Further, a hard coat layer described in paragraphs 0097 to 0113 of JP-A-2012-215689 may be further laminated on the resin film.
• optical member Another form of the optical member is an optical member having a laminate of a support and a resin layer.
• this optical member at least one of the support and the resin layer contains the cured product of the present invention described above.
• the thickness of the resin layer in the laminate is preferably 1 ⁇ m to 2500 ⁇ m, more preferably 10 ⁇ m to 500 ⁇ m.
• the support in the laminate is preferably a material having transparency within a range that does not impair the optical performance. That the support is transparent means that it is optically transparent, and specifically means that the total light transmittance of the support is 85% or more.
• the total light transmittance of the support is preferably 90% or more, more preferably 95% or more.
• a suitable example of the support is a resin film.
• Resins constituting the resin film include ester resins (e.g., polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polycyclohexanedimethylene terephthalate (PCT), etc.), olefin resins (e.g., polypropylene (PP), polyethylene (PE), etc.), polyvinyl chloride (PVA), tricellulose acetate (TAC), and the like.
• PET is preferable in terms of versatility.
• the thickness of the support can be appropriately selected according to the application or purpose. Generally, the thickness is preferably 5 ⁇ m to 2500 ⁇ m, more preferably 20 ⁇ m to 500 ⁇ m.
• a peelable support can also be used as the support.
• Such laminates are preferably used for polarizing plates and the like.
• the peelable support means a support that can be peeled off from the resin film.
• the stress when peeling the support from the resin film is preferably 0.05 N/25 mm or more and 2.00 N/25 mm or less, more preferably 0.08 N/25 mm or more and 0.50 N/25 mm or less, More preferably, it is 0.11 N/25 mm or more and 0.20 N/25 mm or less.
• the stress at the time of peeling the support from the resin film was measured by a tensile test after the surface of the laminate cut into a width of 25 mm and a length of 80 mm was pasted and fixed to the glass substrate via an acrylic pressure-sensitive adhesive sheet.
• a machine RDF-1210 manufactured by A&D Co., Ltd.
• one end of the test piece in the length direction was gripped, and the temperature was 23 ° C. and the relative humidity was 60%.
• Grip movement speed 200 mm/min
• 90° peeling test (Complies with Japanese Industrial Standards (JIS) K 6854-1: 1999 "Adhesives - Peeling strength test method - Part 1: 90 degree peeling" was evaluated by implementing
• the peelable support one containing polyethylene terephthalate (PET) as a main component (a component having the largest content on a mass basis among the components constituting the support) is preferable.
• PET polyethylene terephthalate
• the weight average molecular weight of PET is preferably 20,000 or more, more preferably 30,000 or more, and even more preferably 40,000 or more.
• the weight average molecular weight of PET can be determined by dissolving the support in hexafluoroisopropanol (HFIP) and performing the GPC method described above.
• the thickness of the support is not particularly limited, but is preferably 0.1 to 100 ⁇ m, more preferably 0.1 to 75 ⁇ m, even more preferably 0.1 to 55 ⁇ m, and 0.1 ⁇ 10 ⁇ m is particularly preferred.
• the support may also be subjected to known surface treatments such as corona treatment, glow discharge treatment, undercoating, and the like.
• optical member is a laminate having a hard coat layer, a transparent support, and an adhesive layer or adhesive layer laminated in this order.
• a laminate is preferably used as an ultraviolet cut filter or protective material (protective film, protective sheet).
• any one of the support, the hard coat layer, and the pressure-sensitive adhesive layer or adhesive layer may contain the cured product of the present invention described above.
• a hard coat layer for example, JP-A-2013-045045, JP-A-2013-043352, JP-A-2012-232459, JP-A-2012-128157, JP-A-2011-131409, JP-A-2011 -131404, JP 2011-126162, JP 2011-075705, JP 2009-286981, JP 2009-263567, JP 2009-075248, JP 2007-164206 JP, JP 2006-096811, JP 2004-075970, JP 2002-156505, JP 2001-272503, WO 2012/018087, WO 2012/098967 , WO 2012/086659 and WO 2011/105594 can be applied.
• the thickness of the hard coat layer is preferably 5 to 100 ⁇ m from the viewpoint of further improving scratch resistance.
• the optical member of this form has an adhesive layer or adhesive layer on the side opposite to the side of the supporting substrate having the hard coat layer.
• the type of pressure-sensitive adhesive or adhesive used for the pressure-sensitive adhesive layer or adhesive layer is not particularly limited, and known pressure-sensitive adhesives or adhesives can be used.
• the pressure-sensitive adhesive or adhesive includes acrylic resins described in paragraph numbers 0056 to 0076 of JP-A-2017-142412 and crosslinking agents described in paragraph numbers 0077-0082 of JP-A-2017-142412. is also preferred.
• the pressure-sensitive adhesive or adhesive is an adhesion improver (silane compound) described in paragraph numbers 0088 to 0097 of JP-A-2017-142412, and an addition described in paragraph number 0098 of JP-A-2017-142412. agent.
• the adhesive layer or adhesive layer can be formed by the method described in paragraphs 0099 to 0100 of JP-A-2017-142412.
• the thickness of the adhesive layer or adhesive layer is preferably 5 ⁇ m to 100 ⁇ m from the viewpoint of both adhesive strength and handling properties.
• 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 cured product of the present invention in members such as antireflection films, polarizing plate protective films, optical films, retardation films, adhesives, and adhesives.
• the optical member containing the cured product of the present invention may be arranged on either the viewer side (front side) or the backlight side with respect to the liquid crystal cell, and the side far from the liquid crystal cell with respect to the polarizer (outer side). ), as well as on the near side (inner).
• Organic electroluminescent display devices include optical films, polarizing plate protective films in circularly polarizing plates, retardation films such as quarter-wave plates, adhesives, adhesives, and other members containing the cured product of the present invention.
• An electroluminescent display device is mentioned.
• At least one of R 11 , R 12 , Q 3 and Q 4 among the compounds represented by the above formula (3) is a group containing a polymerizable group having an ethylenically unsaturated bond. It includes a structure derived from a compound having a certain structure (hereinafter also referred to as structure (3)).
• structure (3) a structure derived from a compound having a certain structure
• at least one of R 11 , R 12 , Q 3 and Q 4 is a group containing a polymerizable group having an ethylenically unsaturated bond. It is also called a specific compound (3).
• the polymer of the present invention is a compound (hereinafter also referred to as other polymerizable compound) having an ethylenically unsaturated bond-containing group other than the specific compound (3), in addition to the structure derived from the specific compound (3) described above. It may also contain the structure of origin. That is, the polymer of the present invention may form a copolymer with the specific compound (3) and another polymerizable compound.
• other polymerizable compounds include the polymerizable compounds described as materials used in the resin composition of the present invention, compounds having polymerizable groups described as materials used as other ultraviolet absorbers, and the like.
• the content of the structure derived from the specific compound (3) in the polymer of the present invention is preferably 0.01 to 100% by mass.
• the upper limit is more preferably 50% by mass or less, and even more preferably 10% by mass or less.
• the lower limit is more preferably 0.02% by mass or more, and even more preferably 0.1% by mass or more.
• the number weight average molecular weight of the polymer of the present invention is preferably 5,000 to 80,000, more preferably 10,000 to 60,000, even more preferably 10,000 to 40,000.
• the polymer of the present invention can be used for ultraviolet absorbers, optical members, and the like.
• the polymer of the present invention can also be used by mixing with a resin.
• examples of the resin include the resins described in the section of the resin composition of the present invention.
• intermediate 1-2 was synthesized according to the following synthetic scheme. 50 g of intermediate 1-1, 24.5 g of 2,3-dichloro-5,6-dicyano-p-benzoquinone, and 500 ml of tetrahydrofuran were added and mixed, followed by stirring at 20° C. for 1 hour. After completion of the reaction, 500 mL of hexane was added, and the precipitated solid was collected by filtration and washed with 150 mL of hexane to obtain 42 g of intermediate 1-2 (yield: 84%).
• Intermediate 1-3 was synthesized according to the following synthetic scheme. 30 g of intermediate 1-2, 8 g of piperidinium pentamethylenedithiocarbamate, 360 mL of N-methyl-2-pyrrolidone, 160 mL of acetic acid, and 54 mL of acetone were added and mixed, followed by stirring at 60° C. for 1 hour. bottom. The precipitated solid was collected by filtration and washed with 300 ml of acetone to obtain 8.0 g of Intermediate 1-3 (yield 36%).
• Synthesis Example 32 Synthesis of compound A-142 In Synthesis Example 31, the same method as in Synthesis Example 3 except that 3,5,5-trimethylhexanoyl chloride is used instead of 2-ethylhexanoyl chloride. to obtain 2.1 g of compound A-143 (yield 60%).
• ⁇ Test Example 1> After dissolving 2 mg of the compounds described in the table below (exemplary compounds (1) to (44), comparative compounds (1) to (3)) in 100 mL of ethyl acetate, the absorbance of the solution is 0.6 to 1.2. Sample solutions 101-147 were prepared by diluting with ethyl acetate to fill the range. The absorbance and molar extinction coefficient of each sample solution were 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, and the long-wavelength ultraviolet absorption ability was evaluated according to the following criteria.
• the ratio of absorbance at a wavelength of 440 nm to 1 at a wavelength of 400 nm was calculated, and the colorability was evaluated according to the following criteria.
• a smaller value of the absorbance ratio A 440 means less coloring.
• the evaluation results are shown in the table below.
• the numerical value in parentheses in the column of long-wavelength ultraviolet absorption capacity is the value of ⁇ max
• the numerical value in parentheses in the column of coloring property is the value of absorbance ratio A440 .
• the values of molar absorption coefficients at the maximum absorption wavelengths are shown in the column of molar absorption coefficients in the table below.
• ⁇ max is 390 nm or more
• B ⁇ max is 370 nm or more and less than 390 nm
• C ⁇ max is less than 370 nm
• the sample solutions 101 to 144 using the exemplary compounds (1) to (44) were excellent in long-wavelength ultraviolet absorption ability and colorability.
• the obtained resin composition was spin-coated on a glass substrate to form a coating film, and the obtained coating film was dried at 110° C. for 2 minutes to prepare resin films 201 to 251 .
• the absorbance of the resin films 201 to 251 was measured using a spectrophotometer (UV-1800PC, manufactured by Shimadzu Corporation).
• the maximum absorption wavelength ( ⁇ max ) was measured from the spectrum chart obtained for each resin film, and the long-wavelength ultraviolet absorption ability was evaluated according to the same criteria as in Test Example 1.
• the ratio of absorbance at a wavelength of 440 nm to 1 at a wavelength of 400 nm was calculated, and the colorability was evaluated according to the same criteria as in Test Example 1.
• the evaluation results are shown in the table below.
• the numerical value in parentheses in the column of long-wavelength ultraviolet absorption capacity is the value of ⁇ max
• the numerical value in parentheses in the column of coloring property is the value of absorbance ratio A440 .
• the resin films 201 to 251 were subjected to a light resistance test under Condition 1 below, and the light resistance was evaluated by obtaining the absorbance maintenance rate at the maximum absorption wavelength ( ⁇ max ). Specifically, after measuring the absorbance at ⁇ max of the resin film using a spectrophotometer (UV-1800PC, manufactured by Shimadzu Corporation), the resin film was subjected to a light resistance test for 3 weeks under condition 1, The absorbance at ⁇ max was measured for the resin film after the light resistance test. Next, using the absorbance values at ⁇ max of the resin film before and after the light resistance test, the absorbance retention rate (%) was calculated from the following formula, and the light resistance was evaluated according to the following criteria.
• ⁇ max maximum absorption wavelength
• the resin films 201 to 248 using the exemplary compounds (1) to (44) were excellent in long-wavelength ultraviolet absorption ability, colorability, and light resistance.
• a resin composition (photopolymerizable composition) was prepared by mixing the following components.
• UV absorber (compounds listed in the table below).
• KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., compound having two or more ethylenically unsaturated bond-containing groups).
• KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., compound having two or more ethylenically unsaturated bond-containing groups.
• KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., compound having two or more ethylenically unsaturated bond-containing groups.
• ⁇ 2.8 parts by mass Resin Dianal BR-80 (manufactured by Mitsubishi Chemical Corporation)
• Photopolymerization initiator compound described in the table below
• Solvent propylene glycol monomethyl ether acetate
• V-1 Irgacure OXE01 (manufactured by BASF, oxime compound, photoradical polymerization initiator)
• V-2 Omnirad 2959 (manufactured by IGM Resins B.V., hydroxyacetophenone compound, photoradical polymerization initiator)
• V-3 Omnirad TPO (manufactured by IGM Resins B.V., acylphosphine compound, photoradical polymerization initiator)
• the above resin composition is spin-coated onto a 50 mm ⁇ 50 mm glass substrate (1737, manufactured by Corning) so that the film thickness after forming the film is 1.5 ⁇ m, and dried at 120 ° C. for 5 minutes. A composition layer was formed. After that, the entire surface of the resin composition layer was exposed to light with an exposure amount of 1000 mJ/cm 2 using an i-line stepper exposure device (UX-1000SM-EH04, manufactured by Ushio Inc.) to obtain resin films 301 to 330. manufactured.
• the degree of change in transmittance (change in transmittance 1) at the maximum absorption wavelength ( ⁇ max ) of the resin composition layer before and after exposure was 5% or less.
• the light resistance was evaluated by obtaining the absorbance maintenance rate at the maximum absorption wavelength ( ⁇ max ) under Condition 2 below. Specifically, after measuring the absorbance at ⁇ max of the resin film using a spectrophotometer (UV-1800PC, manufactured by Shimadzu Corporation), the resin film was subjected to a light resistance test for 3 days under condition 2, The absorbance at ⁇ max was measured for the resin film after the light resistance test. Next, using the absorbance values at ⁇ max of the resin film before and after the light resistance test, the absorbance retention rate (%) was calculated from the following formula, and the light resistance was evaluated according to the following criteria. It means that the higher the absorbance retention rate, the better the light resistance.
• exemplary compounds (1), (18), (28), (29), (30), (32), (33), (40), (41), (42), ( 43) were excellent in light resistance.
• the resin films 301 to 321 were excellent in the ability to absorb ultraviolet light having a wavelength of about 400 nm, and were less colored.
• the resin films 301 to 321 were stored for one week under conditions of 40°C and 50% humidity, and then left at room temperature for one day to visually observe the presence or absence of bleeding out and precipitation. Bleed-out and deposition were not observed in any of the resin films 301-321.
• compositions 401-424, 432-437 Compositions (photopolymerizable compositions) 401 to 424 and 432 to 437 were prepared by mixing the following components.
• Ultraviolet absorber compound listed in the table below..2.0 parts by mass Polymerizable compound (compound listed in the table below)...2.6 parts by mass Resin (resin listed in the table below)... 12.9 parts by mass Photopolymerization initiator (compounds listed in the table below)...2.5 parts by mass Solvent (propylene glycol monomethyl ether acetate)...40.0 parts by mass Solvent (cyclopentanone)...
• composition (photopolymerizable composition) 425 was prepared by mixing the following components.
• UV absorber (exemplified compound (1)) 2.0 parts by mass Polymerizable compound T-2 0.5 parts by mass Polymerizable compound T-4 1.5 parts by mass Resin U-3 ... 13.5 parts by mass Photopolymerization initiator V-8 ... 2.5 parts by mass Solvent (toluene) ... 80.0 parts by mass Surfactant (KF-6001, manufactured by Shin-Etsu Chemical Co., Ltd. , carbinol-modified polydimethylsiloxane at both ends, hydroxyl value 62 mgKOH/g) 0.02 parts by mass
• composition (photopolymerizable composition) 426 was prepared by mixing the following components.
• UV absorber (exemplified compound (1)) 2.0 parts by mass Polymerizable compound T-6 10.5 parts by mass Polymerizable compound T-1 5.0 parts by mass Photopolymerization initiator V-1: 2.2 parts by mass Photopolymerization initiator V-5: 0.3 parts by mass Solvent (ethyl acetate): 40.0 parts by mass Solvent (cyclopentanone): 40.
• composition (photopolymerizable composition) 427 was prepared by mixing the following components.
• UV absorber (exemplified compound (1)) 2.0 parts by mass Polymerizable compound T-5 5.0 parts by mass Polymerizable compound T-4 4.0 parts by mass Resin U-1 6.5 parts by mass Photoinitiator V-1 2.0 parts by mass Photoinitiator V-6 0.5 parts by mass Solvent (ethyl acetate) 40.0 parts by mass Part solvent (cyclopentanone) ... 40.0 parts by mass Surfactant (KF-6001, manufactured by Shin-Etsu Chemical Co., Ltd., carbinol-modified polydimethylsiloxane at both ends, hydroxyl value 62 mgKOH / g) ... 0 .02 parts by mass
• composition (photopolymerizable composition) 428 was prepared by mixing the following components.
• UV absorber (exemplified compound (1)) 2.0 parts by mass Polymerizable compound T-7 60 parts by mass Polymerizable compound T-8 25 parts by mass Polymerizable compound T-9 . ⁇ 15 parts by mass Photopolymerization initiator V-9 ... 8.0 parts by mass
• compositions 429 to 431 were prepared in the same manner as composition 428 except that the same amount of the ultraviolet absorber in composition 428 was changed to exemplified compound (18), exemplified compound (33) or exemplified compound (42).
• T-1 KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a compound having two or more ethylenically unsaturated bond-containing groups)
• T-2 NK ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd., a compound having two or more ethylenically unsaturated bond-containing groups)
• T-3 Light acrylate DCP-A (manufactured by Kyoeisha Chemical Co., Ltd., a compound having two or more ethylenically unsaturated bond-containing groups)
• T-4 benzyl methacrylate
• T-5 Beamset 577 (3- to 6-functional urethane acrylate, manufactured by Arakawa Chemical Industries, Ltd.)
• T-6 FA-512M (dicyclopentenyloxyethyl methacrylate, manufactured by Showa Denko Materials Co., Ltd.)
• T-7 Cychromer M100 (3
• V-1 Omnirad TPO (manufactured by IGM Resins B.V., photoradical polymerization initiator, acylphosphine compound)
• V-2 Omnirad 2959 (manufactured by IGM Resins B.V., photoradical polymerization initiator, hydroxyacetophenone compound)
• V-3 4,4'-bis (diethylamino) benzophenone (photoradical polymerization initiator, benzophenone compound)
• V-4 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (o-Cl-HABI) (photoradical polymerization initiator, hexaarylbiimidazole compounds)
• V-5 IRGACURE-OXE01 (manufactured by BASF, photoradical polymerization initiator, oxime compound)
• V-6 Omnirad 907 manufactured by IGM Resin
• compositions 401 to 435 were formed on a 50 mm ⁇ 50 mm glass substrate (1737, manufactured by Corning) to a thickness of 1 after film formation. It was applied by spin coating so as to have a thickness of 0.5 ⁇ m and dried at 100° C. for 2 minutes to form a composition layer. After that, the entire surface of the composition layer was exposed with an exposure amount of 1000 mJ/cm 2 using an i-line stepper exposure device (UX-1000SM-EH04, manufactured by Ushio Inc.). Then, the resin films 401 to 432 were manufactured by heating (post-baking) at 200° C.
• the degree of change in transmittance (change in transmittance 1) at the maximum absorption wavelength ( ⁇ max ) of the composition layer before and after exposure and post-baking The degree of change in transmittance (change in transmittance 2) at the maximum absorption wavelength ( ⁇ max ) of the composition layers before and after each was 1% or less.
• the resin films 401 to 434 using the exemplary compounds (1), (18), (33), (42), and (43) had excellent light resistance. Moreover, the resin films 401 to 434 were excellent in the ability to absorb ultraviolet light having a wavelength of about 400 nm, and were less colored.
• Synthesis of Polymer P-1 100 mg of compound A-142 (maximum absorption wavelength (in ethyl acetate solution): 394 nm) obtained in Synthesis Example 32, 9.9 g of methyl methacrylate, and 40.0 g of propylene glycol monomethyl ether acetate were added to a 200 mL three-necked flask. , and stirred at 80° C. for 30 minutes under a nitrogen stream. 200 mg of 2,2′-azobis(isobutyrate)dimethyl (V-601, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
• V-601 (hereinafter referred to as V-601)) was added to this solution and stirred at 80° C. for 6 hours. After that, it was cooled to room temperature. The resulting reaction mixture was slowly added to a mixture of 140 mL of hexane and 60 mL of isopropyl alcohol and allowed to stand overnight. The deposited precipitate was collected by filtration and washed with a mixture of hexane and isopropyl alcohol. 140 mL of hexane and 60 mL of isopropyl alcohol were added to the obtained powder, and the mixture was stirred at room temperature for 1 hour and then allowed to stand at room temperature overnight.
• the precipitate was collected by filtration, washed with a mixture of hexane and isopropyl alcohol, and dried at 50° C. to obtain 7.0 g of the desired polymer P-1.
• the obtained polymer P-1 had a number average molecular weight of 27,500 (converted to polystyrene).
• 100 mg of the obtained polymer P-1 was dissolved in 100 mL of chloroform, and the absorption spectrum was measured.
• the maximum absorption wavelength of polymer P-1 was 399 nm (absorbance 1.61).
• the polymer P-1 was able to sufficiently block light with a wavelength around 400 nm. Moreover, the polymer P-1 was slightly colored.
• the resulting reaction mixture was slowly added to a mixture of 140 mL of hexane and 60 mL of isopropyl alcohol and allowed to stand overnight.
• the deposited precipitate was collected by filtration and washed with a mixture of hexane and isopropyl alcohol.
• 140 mL of hexane and 60 mL of isopropyl alcohol were added to the obtained powder, and the mixture was stirred at room temperature for 1 hour and then allowed to stand at room temperature overnight.
• the precipitate was collected by filtration, washed with a mixture of hexane and isopropyl alcohol, and dried at 50° C. to obtain 5.0 g of the desired polymer P-2.
• the obtained polymer P-2 had a number average molecular weight of 33,400 (converted to polystyrene). 150 mg of the obtained polymer P-2 was dissolved in 100 mL of chloroform, and the absorption spectrum was measured. The maximum absorption wavelengths of polymer P-2 were 399 nm (absorbance 1.45) and 343 nm (absorbance 0.83). The polymer P-2 was able to sufficiently block light with a wavelength around 400 nm. Furthermore, it was also excellent in shielding properties for light with a wavelength shorter than 350 nm. Moreover, the polymer P-2 was slightly colored.
• Lazolidin-4-ylidene)-5-methylbenzo[d][1,3]dithiol-4,7-diylbis((2-(methacryloyloxy)ethyl)succinate) (maximum absorption wavelength (in ethyl acetate solution): 380 nm ), 9.8 g of methyl methacrylate, and 40.0 g of propylene glycol monomethyl ether acetate were added, stirred at 80° C. for 6 hours under a nitrogen stream, and then cooled to room temperature. The resulting reaction mixture was slowly added to a mixture of 140 mL of hexane and 60 mL of isopropyl alcohol and allowed to stand overnight.
• the deposited precipitate was collected by filtration and washed with a mixture of hexane and isopropyl alcohol. 140 mL of hexane and 60 mL of isopropyl alcohol were added to the obtained powder, and the mixture was stirred at room temperature for 1 hour and then allowed to stand at room temperature overnight. The precipitate was collected by filtration, washed with a mixture of hexane and isopropyl alcohol, and dried at 50° C. to obtain 6.1 g of the desired polymer P-3. The obtained polymer P-3 had a number average molecular weight of 38,200 (converted to polystyrene).
• polymer P-3 150 mg was dissolved in 100 mL of chloroform, and the absorption spectrum was measured.
• the maximum absorption wavelengths of polymer P-3 were 399 nm (absorbance 2.12) and 383 nm (absorbance 0.80).
• the polymer P-3 was able to sufficiently block light with a wavelength around 400 nm. Furthermore, it was also excellent in shielding properties for light with a wavelength shorter than 350 nm. Moreover, the polymer P-3 was slightly colored.
• Synthesis Example 104 Synthesis of Polymer P-4 In a 200 mL three-necked flask, 180 mg of compound A-142 (maximum absorption wavelength (in ethyl acetate solution): 394 nm) obtained in Synthesis Example 32, and bis(2-(methacryloyloxy)ethyl) 4,4' as an ultraviolet absorber.
• the resulting reaction mixture was slowly added to a mixture of 140 mL of hexane and 60 mL of isopropyl alcohol and allowed to stand overnight.
• the deposited precipitate was collected by filtration and washed with a mixture of hexane and isopropyl alcohol.
• 140 mL of hexane and 60 mL of isopropyl alcohol were added to the obtained powder, and the mixture was stirred at room temperature for 1 hour and then allowed to stand at room temperature overnight.
• the precipitate was collected by filtration, washed with a mixture of hexane and isopropyl alcohol, and dried at 50° C. to obtain the target polymer P-4 in 5.8. I got g.
• the obtained polymer P-4 had a number average molecular weight of 31,900 (converted to polystyrene). 150 mg of the obtained polymer P-4 was dissolved in 100 mL of chloroform, and the absorption spectrum was measured. The maximum absorption wavelengths of polymer P-4 were 399 nm (absorbance 2.31) and 390 nm (absorbance 0.78). The polymer P-4 was able to sufficiently shield light with a wavelength around 400 nm. Furthermore, it was also excellent in shielding properties for light with a wavelength shorter than 350 nm. Moreover, the polymer P-4 was slightly colored.
• the obtained polymer P-5 had a number average molecular weight of 29,500 (converted to polystyrene). 100 mg of the obtained polymer P-5 was dissolved in 100 mL of chloroform, and the absorption spectrum was measured. The maximum absorption wavelength of polymer P-5 was 397 nm (absorbance 1.57). The polymer P-5 was able to sufficiently shield light with a wavelength around 400 nm. Further, the polymer P-5 was slightly colored.
• the resulting reaction mixture was slowly added to a mixture of 140 mL of hexane and 60 mL of isopropyl alcohol.
• the deposited precipitate was collected by filtration and washed with a mixture of hexane and isopropyl alcohol.
• 140 mL of hexane and 60 mL of isopropyl alcohol were added to the obtained powder, and after stirring at room temperature for 3 hours, the precipitate was collected by filtration, washed with a mixture of hexane and isopropyl alcohol, and dried at 50°C to obtain the desired polymer P.
• 8.1 g of -6 was obtained.
• the obtained polymer P-5 had a number average molecular weight of 14,100 (converted to polystyrene).
• polymer P-6 150 mg was dissolved in 100 mL of chloroform, and the absorption spectrum was measured.
• the maximum absorption wavelength of polymer P-6 was 339 nm (absorbance 0.91).
• Polymer P-6 had a low shielding property against light with a wavelength of 380 to 400 nm.
• Example 5> Production of resin film 501 500 mg of polymer P-1, 7.6 g of chloroform, and polymethyl methacrylate resin (Dianal BR-80 (containing 60% by mass or more of methyl methacrylate as a monomer unit, weight average molecular weight : 95000, acid value: 0 mgKOH/g, manufactured by Mitsubishi Chemical Co., Ltd.) to prepare a resin composition (resin solution) by dissolving 1.1 g. The obtained resin composition was spin-coated on a glass substrate. Then, the coating film was dried at 60° C. for 2 minutes to form a resin film 501 containing the polymer P-1 and having a thickness of about 10 ⁇ m. Excellent light shielding properties.
• Example 502 Production of resin film 502
• Resin film 502 was formed in the same manner as in Example 501, except that 500 mg of polymer P-1 was changed to 500 mg of polymer P-2. .
• the resin film 502 had almost no coloration and was excellent in blocking light with a wavelength around 400 nm. Furthermore, it was also excellent in shielding properties for light with a wavelength shorter than 350 nm.
• Example 503 Production of resin film 503
• Resin film 503 was formed in the same manner as in Example 501, except that 500 mg of polymer P-1 was changed to 500 mg of polymer P-3. .
• the resin film 503 had almost no coloration and was excellent in blocking light with a wavelength around 400 nm. Furthermore, it was also excellent in shielding properties for light with a wavelength shorter than 350 nm.
• Example 504 Production of resin film 504
• Resin film 504 was formed in the same manner as in Example 501, except that 500 mg of polymer P-1 was changed to 500 mg of polymer P-4. .
• the resin film 504 had almost no coloration and was excellent in blocking light with a wavelength around 400 nm. Furthermore, it was also excellent in shielding properties for light with a wavelength shorter than 350 nm.
• Example 505 Production of resin film 505
• Resin film 505 was formed in the same manner as in Example 501, except that 500 mg of polymer P-1 was changed to 500 mg of polymer P-5.
• the resin film 505 had almost no coloration and was excellent in blocking light with a wavelength around 400 nm. Furthermore, it was also excellent in shielding properties for light with a wavelength shorter than 350 nm.
• a resin film 506 was formed in the same manner as in Example 501, except that 500 mg of polymer P-1 was changed to 1063 mg of polymer P-6.
• the resin film of the resin film 506 had a low shielding property for light with a wavelength of 380 to 400 nm.
• Apparatus Low-temperature cycle xenon weather meter (Suga Test Instruments Co., Ltd.: XL75) Illuminance: 90 klx (40 w/m 2 ) Time: 3 weeks Environment: 23°C, 5% relative humidity
• the resin films 501-505 (Examples 501-505) were excellent in light resistance. Moreover, the resin films 501 to 505 were excellent in the ability to absorb ultraviolet light having a wavelength of about 400 nm, and were less colored.
• the resin films 501 to 505 were stored for one week under conditions of 40°C and 50% humidity, and then left at room temperature for one day to visually observe the presence or absence of bleeding out and precipitation. Bleed-out and deposition were not confirmed in any of the resin films 501-505.
• the resin films 601 to 608 were subjected to a light resistance test under condition 5 below, and the absorbance retention rate at the maximum absorption wavelength ( ⁇ max ) was obtained to evaluate the light resistance. Specifically, after measuring the absorbance at ⁇ max of the resin film using a spectrophotometer (UV-1800PC, manufactured by Shimadzu Corporation), the resin film was subjected to a light resistance test under condition 5, and the light resistance was The absorbance at ⁇ max was measured for the resin film after the test. Next, using the absorbance values at ⁇ max of the resin film before and after the light resistance test, the absorbance retention rate (%) was calculated from the following formula, and the light resistance was evaluated according to the following criteria.
• the resin films 601 to 605 using the exemplary compounds (1), (18), (33), (42), and (43) had excellent light resistance. Moreover, the resin films 601 to 605 were excellent in the ability to absorb ultraviolet light having a wavelength of about 400 nm, and were less colored.
• the resin films 601 to 605 were stored for one week under conditions of 40°C and 50% humidity, and then left at room temperature for one day to visually observe the presence or absence of bleeding out and precipitation. Bleed-out and precipitation were not confirmed in any of the resin films 601-605.
• the resin films 701 to 725 using the exemplary compounds (1), (18), (33), (42), and (43) had excellent light resistance. Moreover, the resin films 701 to 725 were excellent in the ability to absorb ultraviolet light having a wavelength of about 400 nm, and were less colored.
• the resin films 701 to 725 were stored for one week under conditions of 40°C and 50% humidity, and then left at room temperature for one day to visually observe the presence or absence of bleeding out and precipitation. Bleed-out and deposition were not confirmed in any of the resin films 701-725.
• a (meth)acrylic resin Dianal BR-80, manufactured by Mitsubishi Chemical Corporation, containing 60% by mass or more of methyl methacrylate as a monomer unit, weight average molecular weight of 95,000
• the resin films 801 to 815 were subjected to a light resistance test under condition 6 below, and the light resistance was evaluated by obtaining the absorbance retention rate at a wavelength of 400 nm. Specifically, after measuring the absorbance of the resin film at ⁇ max using a spectrophotometer (UV-1800PC, manufactured by Shimadzu Corporation), the resin film was subjected to a light resistance test for 3 weeks under condition 6, The absorbance at ⁇ max was measured for the resin film after the light resistance test. Next, using the absorbance values at ⁇ max of the resin film before and after the light resistance test, the absorbance retention rate (%) was calculated from the following formula, and the light resistance was evaluated according to the following criteria. It means that the higher the absorbance retention rate, the better the light resistance.
• the resin films 801 to 815 had a large absorption of light in the vicinity of a wavelength of 400 nm, and were excellent in the absorption of ultraviolet rays on the long wavelength side. In addition, the absorbance retention rate at 400 nm after the light resistance test was also good, indicating excellent light resistance.
• Exemplary compounds (1), (18), (33), (42), and (43) in the above table are compounds having the structures described above.
• Compounds C-1 to C-3 are compounds having the following structures.

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