JP7128633B2 - Resin composition and optical filter - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition containing an ultraviolet absorber and an optical filter having a resin layer formed from the resin composition.

Conventionally, a resin composition containing an ultraviolet absorber, an optical film formed from the resin composition, and the like are known (eg, Patent Documents 1 to 4). Such a resin composition can suppress deterioration due to ultraviolet rays, and can also be applied as a resin composition for forming an optical filter that absorbs light in the ultraviolet to violet region.

JP 2013-190553 A JP 2010-100787 A JP-A-2003-26942 JP-A-2003-43259

Resin compositions are used by being molded into various shapes depending on the intended use. A thin optical filter can be obtained. When a resin layer is formed by coating a resin composition on a substrate in this way, it is preferable to increase the adhesion between the resin layer and the substrate and integrate them as much as possible. Especially in an optical filter, if a gap occurs between the resin layer and the substrate, the refractive index may change and the desired optical performance may not be obtained. important. At this time, it is desirable that the adhesion between the resin layer and the substrate is maintained even under severe conditions.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resin composition containing an ultraviolet absorber, which is used to form a resin layer on a substrate, which is subjected to severe An object of the present invention is to provide a resin composition capable of ensuring adhesion of a resin layer to a substrate even under difficult conditions, and an optical filter formed from the resin composition.

［式（１）中、
Ｒ¹はシアノ基、アシル基、カルボン酸エステル基またはアミド基を表し、
Ｒ²は水素原子、シアノ基、アシル基、カルボン酸エステル基、アミド基、炭化水素基またはヘテロアリール基を表し、
Ｒ¹とＲ²がともにアシル基、カルボン酸エステル基またはアミド基である場合、Ｒ¹とＲ²は互いに連結して環を形成していてもよく、
Ｒ³は水素原子またはアルキル基を表し、
Ｒ⁴は水素原子、有機基または極性官能基を表し、複数のＲ⁴は互いに同一または異なっていてもよく、
Ｒ⁵は有機基を表し、
Ｘは硫黄原子または酸素原子を表す。］
［５］さらに（Ｄ）近赤外吸収色素および／または可視光吸収色素を含有する［１］～［４］のいずれかに記載の樹脂組成物。
［６］基板と、前記基板上に形成され、［１］～［５］のいずれかに記載の樹脂組成物を硬化した樹脂層とを有することを特徴とする光学フィルター。
［７］［６］に記載の光学フィルターを備えることを特徴とするセンサー。 The present invention includes the following inventions.
[1] (A) a thermoplastic resin, (B) an epoxy group-containing silane coupling agent, a hydrolyzate thereof, and at least one selected from the group consisting of a hydrolytic condensate thereof, and (C) an ether bond and/or Or a resin composition characterized by containing an ultraviolet absorber having a thioether bond.
[2] The resin composition according to [1], which contains a hydrolyzate and/or a hydrolyzed condensate of an epoxy group-containing silane coupling agent as the component (B).
[3] The resin composition according to [1] or [2], wherein the UV absorber of component (C) has at least a thioether bond.
[4] The resin composition according to any one of [1] to [3], wherein the UV absorber of component (C) is a compound represented by the following formula (1).

[In formula (1),
R ¹ represents a cyano group, an acyl group, a carboxylic acid ester group or an amide group;
R ² represents a hydrogen atom, a cyano group, an acyl group, a carboxylic acid ester group, an amide group, a hydrocarbon group or a heteroaryl group;
When both R ¹ and R ² are an acyl group, a carboxylic acid ester group or an amide group, R ¹ and R ² may be linked together to form a ring,
^R3 represents a hydrogen atom or an alkyl group;
R ⁴ represents a hydrogen atom, an organic group or a polar functional group, a plurality of R ⁴ may be the same or different,
R ⁵ represents an organic group,
X represents a sulfur atom or an oxygen atom. ]
[5] The resin composition according to any one of [1] to [4], further comprising (D) a near-infrared absorbing dye and/or a visible light absorbing dye.
[6] An optical filter comprising a substrate and a resin layer formed on the substrate and obtained by curing the resin composition according to any one of [1] to [5].
[7] A sensor comprising the optical filter of [6].

The resin composition of the present invention comprises (A) a thermoplastic resin, (B) at least one selected from an epoxy group-containing silane coupling agent, a hydrolyzate thereof, and a hydrolytic condensate thereof, and (C) an ether Since an ultraviolet absorber having a bond and/or a thioether bond is blended, when a resin layer is formed on a substrate using the resin composition, the adhesion of the resin layer to the substrate can be enhanced. . The resin layer thus formed exhibits excellent adhesion to the substrate not only immediately after forming the resin layer on the substrate, but also after boiling in water under severe conditions. Further, the optical filter in which the resin layer is formed on the substrate in this way has excellent adhesion between the resin layer and the substrate.

The resin composition of the present invention comprises (A) a thermoplastic resin, (B) at least one selected from an epoxy group-containing silane coupling agent, a hydrolyzate thereof, and a hydrolytic condensate thereof, and (C) an ether and a UV absorber having a bond and/or a thioether bond. The resin composition of the present invention contains the above components (A) to (C), so that when a resin layer is formed on a substrate using the resin composition, the adhesion of the resin layer to the substrate is improved. can be enhanced.

The thermoplastic resin used as component (A) is not particularly limited as long as it is a resin that softens when heated. As the thermoplastic resin, it is preferable to use a resin having high transparency. polyethylene resin, polypropylene resin), cycloolefin resin, urethane resin, styrene resin, polyvinyl acetate, polyamide resin (e.g., nylon), aramid resin, polyimide resin, polyamideimide resin, polyester resin (e.g., polybutylene terephthalate ( PBT), polyethylene terephthalate (PET), etc.), butyral resin, polycarbonate resin, polyether resin, polysulfone resin, ABS resin (acrylonitrile butadiene styrene resin), AS resin (acrylonitrile-styrene copolymer), fluorine resin (e.g. , fluorinated aromatic polymer, polytetrafluoroethylene (PTFE), perfluoroalkoxy fluororesin (PFA), fluorinated polyaryletherketone (FPEK), fluorinated polyimide (FPI), fluorinated polyamic acid (FPAA), fluorine polyethernitrile (FPEN), etc.). Among these, (meth)acrylic resins, cycloolefin resins, polyimide resins, polyamideimide resins, polyester resins, polyarylate resins, polyamide resins, polycarbonate resins, polysulfone resins, fluorine Preferred are aromatic polymers.

(Meth)acrylic resin is a polymer having repeating units derived from (meth)acrylic acid or a derivative thereof. A resin having such a property is preferably used. The (meth)acrylic resin preferably has a ring structure in the main chain, for example, a lactone ring structure, a glutaric anhydride structure, a glutarimide structure, a maleic anhydride structure, a carbonyl group-containing ring structure such as a maleimide ring structure; Carbonyl group-free ring structures such as ring structures, azetidine ring structures, tetrahydrofuran ring structures, pyrrolidine ring structures, tetrahydropyran ring structures, and piperidine ring structures can be mentioned. In addition, the carbonyl group-containing ring structure includes a structure containing a carbonyl group derivative group such as an imide group. (Meth) acrylic resins having a carbonyl group-containing ring structure, for example, JP-A-2004-168882, JP-A-2008-179677, WO 2005/54311, JP-A-2007-31537, etc. Those described can be used.

The cycloolefin-based resin is a polymer obtained by polymerizing a cycloolefin as at least part of a monomer component, and is not particularly limited as long as it has an alicyclic structure in part of its main chain. Examples of cycloolefin-based resins include Topas (registered trademark) manufactured by Polyplastics, APEL (registered trademark) manufactured by Mitsui Chemicals, Zeonex (registered trademark) and Zeonor (registered trademark) manufactured by Nippon Zeon, and JSR Corporation. Arton (registered trademark) manufactured by Sanyo Denki Co., Ltd., etc. can be used.

Polyimide resin is a polymer containing an imide bond in the repeating unit of the main chain, for example, tetracarboxylic acid dianhydride and diamine are polymerized to obtain polyamic acid, which is dehydrated and cyclized (imidization). It can be manufactured by As the polyimide resin, it is preferable to use aromatic polyimide in which aromatic rings are linked by imide bonds. Examples of polyimide resins include Kapton (registered trademark) manufactured by DuPont, Aurum (registered trademark) manufactured by Mitsui Chemicals, Merdin (registered trademark) manufactured by Saint-Gobain, and TPS (registered trademark) TI3000 series manufactured by Toray Plastics Seiko Co., Ltd. etc. can be used.

A polyamideimide resin is a polymer containing an amide bond and an imide bond in the repeating unit of the main chain. For example, Torlon (registered trademark) manufactured by Solvay Advanced Polymers, Vylomax (registered trademark) manufactured by Toyobo Co., Ltd., and TPS (registered trademark) TI5000 series manufactured by Toray Plastics Seiko Co., Ltd. can be used.

A polyester resin is a polymer containing an ester bond in the repeating unit of the main chain, and can be obtained, for example, by condensation polymerization of a polycarboxylic acid (dicarboxylic acid) and a polyalcohol (diol). Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, etc. For example, OKP series manufactured by Osaka Gas Chemicals, TRN series manufactured by Teijin, Teonex ( registered trademark), Rynite (registered trademark) manufactured by DuPont, Novapex (registered trademark) manufactured by Mitsubishi Chemical Corporation, Nova Duran (registered trademark) manufactured by Mitsubishi Engineering-Plastics, Lumirror (registered trademark) manufactured by Toray Industries, Toraycon ( registered trademark), etc. can be used.

A polyarylate resin is a polymer obtained by condensation polymerization of a dihydric phenol compound and a dibasic acid (e.g., an aromatic dicarboxylic acid such as phthalic acid). and a repeating unit containing Examples of polyarylate resins that can be used include Vectran (registered trademark) manufactured by Kuraray Co., Ltd., U Polymer (registered trademark) and Unifiedr (registered trademark) manufactured by Unitika.

A polyamide resin is a polymer containing an amide bond in the repeating unit of the main chain, and can be obtained, for example, by condensation polymerization of a diamine and a dicarboxylic acid. The polyamide resin may have an aliphatic skeleton in its main chain, and nylon, for example, can be used as such an amide resin. The polyamide resin may have an aromatic skeleton, and an aramid resin is known as such a polyamide resin. Aramid resin is preferably used because it has excellent heat resistance and strong mechanical strength. (registered trademark) and the like can be used.

A polycarbonate resin is a polymer containing a carbonate group (--O--(C=O)--O--) in a repeating unit of the main chain. Polycarbonate resins include Panlite (registered trademark) manufactured by Teijin Limited, Iupilon (registered trademark) manufactured by Mitsubishi Engineering-Plastics Corporation, Novarex (registered trademark), and Zanter (registered trademark) manufactured by Sumika Styron Polycarbonate Co., Ltd. (registered trademark) and the like can be used.

Polysulfone resins are polymers having repeating units containing aromatic rings, sulfonyl groups (--SO ₂ --) and oxygen atoms. Examples of polysulfone resins that can be used include Sumika Excel (registered trademark) PES3600P and PES4100P manufactured by Sumitomo Chemical Co., Ltd., and UDEL (registered trademark) P-1700 manufactured by Solvay Specialty Polymers.

The fluorinated aromatic polymer is a repeat comprising an aromatic ring having one or more fluorine atoms and at least one bond selected from the group consisting of an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond and an ester bond. It is a polymer having a unit, and among these, a polymer essentially containing a repeating unit containing an aromatic ring having one or more fluorine atoms and an ether bond is preferable. As the fluorinated aromatic polymer, for example, those described in JP-A-2008-181121 can be used.

The thermoplastic resin used as the component (A) preferably has high transparency, which makes it easier to apply the resin composition to optical applications. For example, the thermoplastic resin preferably has a total light transmittance of 75% or more, more preferably 80% or more, even more preferably 85% or more at a thickness of 0.1 mm. The upper limit of the total light transmittance of the thermoplastic resin is not particularly limited as long as the total light transmittance is 100% or less. Total light transmittance is measured based on JIS K7105.

The thermoplastic resin preferably has a high glass transition temperature (Tg), which can improve the heat resistance of the resin layer formed from the resin composition. The glass transition temperature of the thermoplastic resin is, for example, preferably 110° C. or higher, more preferably 120° C. or higher, and even more preferably 130° C. or higher. Although the upper limit of the glass transition temperature of the thermoplastic resin is not particularly limited, it is preferably 380° C. or less from the viewpoint of improving the moldability of the resin composition.

The content of component (A) in the resin composition is preferably 45% by mass or more, more preferably 60% by mass or more, still more preferably 75% by mass or more, or 99% by mass, based on 100% by mass of the solid content of the resin composition. % by mass or less is preferable, 97% by mass or less is more preferable, and 95% by mass or less is even more preferable. In addition, when the resin composition contains a solvent, the solid content of the resin composition means the amount of the resin composition excluding the solvent.

In the resin composition, as the component (B), at least one selected from an epoxy group-containing silane coupling agent, a hydrolyzate of an epoxy group-containing silane coupling agent, and a hydrolytic condensate of an epoxy group-containing silane coupling agent. contains By containing the (B) component in the resin composition, together with the (C) component described later, when a resin layer is formed on a substrate using the resin composition, the adhesion of the resin layer to the substrate is improved. can be enhanced.

The present inventors have investigated various types of silane coupling agents to be blended in the resin composition, and found that when a silane coupling agent containing an epoxy group is used, a mercapto group, an amino group, a carboxylic acid group, or the like is used. It was found that the adhesion of the resin layer to the substrate is improved as compared with the case of using a silane coupling agent having In particular, when the epoxy group-containing silane coupling agent is used in combination with component (C), which will be described later, it is clear that not only adhesion under normal conditions but also adhesion after boiling in water, which is a severe condition, can be imparted. Became.

A compound having an epoxy group and an alkoxysilyl group can be used as the epoxy group-containing silane coupling agent. The epoxy group-containing silane coupling agent may contain one or more epoxy groups, and may contain one or more alkoxysilyl groups. may

When the epoxy group-containing silane coupling agent contains only one alkoxysilyl group, an alkoxysilane having an epoxy group represented by the following formula (4) is preferably used as the silane coupling agent.
^{SiR11kR12m (} _OR13 ) _{n (} OH) ⁴ _-kmn (4)

In formula (4), R ¹¹ represents an epoxy group-containing group, R ¹² and R ¹³ each independently represent an alkyl group, k represents an integer of 1 to 3, and m represents an integer of 0 to 2. , n represents an integer of 1 to 3. When k is 2 or more, a plurality of R ¹¹ may be the same or different; when m is 2, a plurality of R ¹² may be the same or different; In the above case, the plurality of ORs ¹³ may be the same or different. R ¹¹ , R ¹² , OR ¹³ and OH are groups directly bonded to Si, respectively.

In formula (4), the epoxy group-containing group for R ¹¹ is not particularly limited as long as it contains an epoxy group, and examples thereof include glycidoxy group-containing groups and cycloalkene oxide (alicyclic epoxy group)-containing groups. A glycidoxy group or a cycloalkene oxide may be bonded to a silicon atom via a linking group such as an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms). Preferably, R ¹¹ contains only one epoxy group. Epoxy-containing groups for R ¹¹ include glycidoxy, 3-glycidoxypropyl, 8-(glycidoxy)-n-octyl, 3,4-epoxycyclohexyl, and 2-(3,4-epoxycyclohexyl). An ethyl group etc. are mentioned. From the viewpoint of enhancing the adhesion of the resin layer to the substrate, it is preferable that the distance between the epoxy group contained in R ¹¹ and the silicon atom is not too far. or bonded to the silicon atom via an alkylene group having 1 to 6 carbon atoms.

In formula (4), the alkyl groups of R ¹² and R ¹³ preferably have 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, still more preferably 1 to 3 carbon atoms. R ¹² preferably includes a methyl group, an ethyl group, an n-propyl group and an isopropyl group. OR ¹³ preferably includes a methoxy group, an ethoxy group, an n-propoxy group and an isopropoxy group.

In formula (4), k is preferably 1 or 2, more preferably 1, which makes it easier to improve the adhesion of the resin layer to the substrate. Further, m is preferably 0 or 1, more preferably 0, and n is preferably 2 or 3.

When the epoxy group-containing silane coupling agent contains a plurality of alkoxysilyl groups, the silane coupling agent may be a polymer type polyfunctional epoxy group-containing silane coupling agent (hereinafter simply referred to as "polymer type silane coupling agent". may be used) can be used. The polymer-type silane coupling agent has a structure in which an epoxy group-containing group and an alkoxysilyl group-containing group are bonded to an organic polymer chain, and contains multiple alkoxysilyl groups and multiple epoxy groups in one molecule. can be done. Note that the organic chain of the polymer-type silane coupling agent does not contain polysiloxane. Since the polymer-type silane coupling agent can have multiple alkoxysilyl groups and epoxy groups in one molecule as described above, many reaction points with the resin and the substrate are formed, and the adhesion of the resin layer to the substrate is improved. can be enhanced. The polymer-type silane coupling agent preferably contains more epoxy groups than alkoxysilyl groups in one molecule, and the molar ratio of epoxy groups/alkoxysilyl groups is preferably 2-5, for example.

The hydrolyzate of the epoxy group-containing silane coupling agent used as component (B) can be obtained by converting the alkoxysilyl groups contained in the silane coupling agent into silanol groups by hydrolysis. In addition, the hydrolytic condensate of the epoxy group-containing silane coupling agent is obtained by dehydrating and condensing the silanol groups contained in the hydrolyzate of the silane coupling agent to form a siloxane bond (--Si--O--Si--). can be obtained by When a silane coupling agent is usually hydrolyzed, a hydrolyzate of the silane coupling agent is obtained, and a dehydration condensation reaction of the silanol groups contained in the hydrolyzate also occurs, resulting in hydrolytic condensation of the silane coupling agent. Things are easy to get.

The hydrolytic condensate of the silane coupling agent may be a dehydration condensate of the hydrolyzate of the silane coupling agent of the same kind, or may be a dehydration condensate of the hydrolyzate of the silane coupling agent of a different kind. . When the hydrolytic condensate of the silane coupling agent is the condensate of the silicon compound represented by the above formula (4), the condensate is represented by the following formula (5).
Si _p O _q R ¹¹ _r R ¹² _s (OR ¹³ ) _t (OH) _u (5)

In the above formula (5), p represents an integer of 2 or more, q represents an integer of p−1 to p, r represents an integer of p to 2p+1, s represents an integer of 0 to p+2, and t represents represents an integer from 0 to p+2, u represents an integer from 0 to p+2, and the upper limit of r+s+t+u is 2p+2. In formula (5), a plurality of R ¹¹ may be the same or different, and when s is 2 or more, a plurality of R ¹² may be the same or different, and t is 2 In the above case, the plurality of ORs ¹³ may be the same or different. R ¹¹ , R ¹² , OR ¹³ and OH are groups directly bonded to Si, respectively.

In formula (5), p is preferably 1,000 or less, more preferably 100 or less, and even more preferably 10 or less, thereby making it easier to improve the compatibility with the resin. u is preferably 1 or more, more preferably 0.5p or more, and even more preferably p or more, which makes it easier to improve the adhesion of the resin layer to the substrate. s is preferably p or less, more preferably 0.5p or less, and even more preferably 0. From the viewpoint of compatibility with the resin and prevention of repelling, r is preferably 2p or less, more preferably 1.5p or less, and even more preferably r=p.

The resin composition may contain only one type of component (B), or may contain two or more types. The resin composition preferably contains at least a hydrolyzate or a hydrolyzed condensate of an epoxy group-containing silane coupling agent as the component (B). It is possible to improve the adhesion after boiling in water, which is a difficult condition. More preferably, component (B) contains at least a hydrolyzate or a hydrolyzed condensate of an alkoxysilane having an epoxy group (for example, the alkoxysilane represented by formula (4) above). In this case, the total content of the hydrolyzate and hydrolyzed condensate of the epoxy group-containing silane coupling agent in 100% by mass of component (B) is preferably 10% by mass or more, more preferably 30% by mass or more, and 50% by mass. % or more is more preferable.

Component (B) more preferably contains a hydrolytic condensate of an alkoxysilane having an epoxy group (for example, the alkoxysilane represented by formula (4) above). The dehydration condensate in this case preferably contains at least a dimer or trimer of an alkoxysilane having an epoxy group. For example, when the weight-average molecular weight of the silane compound used as component (B) is measured, it is preferably equal to or less than the molecular weight of a pentamer (assuming that all alkoxy groups are hydroxyl groups). It is more preferable that the molecular weight is equal to or less than that of the polymer. Specific values of the weight average molecular weight are, for example, preferably 300 or more, preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less.

The content of component (B) in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more, based on 100% by mass of the solid content of the resin composition. It is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. If the component (B) is contained at a content of 0.1% by mass or more in the solid content of 100% by mass of the resin composition, when a resin layer is formed on a substrate using the resin composition, It becomes easy to improve the adhesion of the resin layer to the substrate. On the other hand, even if the component (B) is excessively contained in the resin composition, the effect of increasing the adhesion of the resin layer to the substrate is not much improved. , the content of component (B) is preferably 20% by mass or less. As the content of component (B) based on the thermoplastic resin of component (A), the content of component (B) is preferably 0.5 parts by mass or more, and 1 mass The amount is more preferably 3 parts by mass or more, more preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less.

The content of component (B) in the resin composition can be determined by gas chromatography or high performance liquid chromatography. The silane compound of component (B) contained in the resin composition is quantified for each type by gas chromatography or high-performance liquid chromatography, and the content of component (B) can be determined from the total. As component (B), when a dehydration condensate of a silane coupling agent (oligomer such as a dimer or trimer) is included, gel permeation chromatography analysis or the like is combined to determine the existence form of the dehydration condensate. It can also be used as a basis for judgment. For example, when the epoxy group-containing silane coupling agent is hydrolyzed or further dehydrated and condensed, the remaining amount after hydrolysis or further dehydration condensation is subtracted from the amount of the initially used silane coupling agent, The contents of the hydrolyzate and hydrolyzed condensate can be determined.

The resin composition contains an ultraviolet absorber having an ether bond and/or a thioether bond as component (C). When the resin composition contains an ultraviolet absorber having an ether bond and/or a thioether bond as the component (C), in combination with the component (B) described above, the resin composition can be used to When the resin layer is formed, the adhesion of the resin layer to the substrate can be enhanced. Such an ultraviolet absorber contains a double bond group or an aromatic group normally possessed by the ultraviolet absorber, and an ether bond and/or a thioether bond in one molecule, thereby increasing adhesion between the resin layer and the substrate. It is thought that it acts to enhance sexuality.

By containing an ultraviolet absorber as the component (C), the resin composition can suppress deterioration caused by light in the ultraviolet to violet region, and can be cured to form a resin molding such as a film. Therefore, it can be applied to an optical filter or the like for cutting light in the ultraviolet to violet region. Furthermore, even if the resin composition or resin molding is stored or the optical filter is manufactured or processed (e.g., vapor deposition, mounting, etc.), even if it is exposed to ultraviolet light, the ultraviolet light will be released into the resin component or resin composition. It is possible to protect other contained components (near-infrared absorbing dyes, visible light absorbing dyes, etc., which will be described later) and suppress deterioration of these components.

As the ultraviolet absorber, a compound that shows an absorption peak having an absorption maximum in the wavelength range of 300 nm or more and 420 nm or less when the absorption spectrum is measured is preferably used. The chemical structure of the ultraviolet absorber preferably has an aromatic group, more preferably an aromatic hydrocarbon group such as an aryl group, in addition to the ether bond and thioether bond described above.

The ether bond and thioether bond of the component (C) UV absorber are not included in the UV absorber as part of functional groups such as carboxyl groups and sulfo groups. A group (-C(=O)-), a sulfur atom, an oxygen atom, a nitrogen atom, a phosphorus atom, etc. are not adjacently bonded. An alkylene group or an arylene group is preferably bound to both sides of the ether bond or both sides of the thioether bond, and the alkylene group or arylene group may have a substituent.

From the viewpoint of enhancing the adhesion between the resin layer and the substrate, the component (C) ultraviolet absorber preferably has two or more ether bonds and/or thioether bonds in one molecule. From the same point of view, the UV absorber of component (C) preferably has at least a thioether bond, and more preferably has two or more thioether bonds in one molecule.

As the (C) component UV absorber, a styrenic compound represented by the following formula (1) is preferably shown. The styrenic compound represented by the following formula (1) exhibits a sharp absorption peak in the ultraviolet to violet region, exhibits an excellent ultraviolet absorption effect, and exhibits adhesion of the resin layer to the substrate, especially under harsh conditions. Adhesion after boiling in water can be enhanced.

In formula (1), R ¹ represents a cyano group, acyl group, carboxylic acid ester group or amide group, R ² represents a hydrogen atom, a cyano group, an acyl group, a carboxylic acid ester group, an amide group, a hydrocarbon group or a hetero represents an aryl group, and when both R ¹ and R ² are an acyl group, a carboxylic acid ester group, or an amide group, R ¹ and R ² may be linked to form a ring, and R ³ is a hydrogen atom; or an alkyl group, R ⁴ represents a hydrogen atom, an organic group or a polar functional group, a plurality of R ⁴ may be the same or different, R ⁵ represents an organic group, X is a sulfur atom or an oxygen atom represents

In the styrenic compound of formula (1), the ethylene structure containing R ¹ and R ² functions as a chromophore, and at least R ¹ is an electron-withdrawing group. Both R ¹ and R ² may be electron withdrawing groups. In formula (1), a cyano group, an acyl group, a carboxylic acid ester group, an amide group, a hydrocarbon group, or a heteroaryl group is used as the electron-withdrawing group for R ¹ and R ² . In formula (1), R ¹ (or R ² ) may be in cis or trans position with respect to R ³ .

Acyl groups (alkanoyl groups) for R ¹ and R ² include methanoyl, ethanoyl, propanoyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, and dodecanoyl groups. , tridecanoyl group, tetradecanoyl group, pentadecanoyl group, hexadecanoyl group, heptadecanoyl group, octadecanoyl group, nonadecanoyl group, eicosanoyl group and the like. A part of the hydrogen atoms of the acyl group may be substituted with an aryl group, an alkoxy group, a halogeno group, a hydroxyl group, or the like. The alkyl group in the acyl group may be linear or branched. The number of carbon atoms in the acyl group (the number of carbon atoms excluding substituents) is preferably 2-21, more preferably 2-11, still more preferably 2-6.

The carboxylic acid ester groups of R ¹ and R ² are represented by the formula: *-C(=O)-O-R ^a1 , where * represents the bonding site to the carbon atom of the ethylene double bond in formula (1). . In the formula, R ^a1 represents a hydrocarbon group, preferably an alkyl group, an aryl group or an aralkyl group.

Examples of alkyl groups for R ^a1 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, 2-ethylhexyl group, heptyl group, octyl group, Linear or branched alkyl groups such as nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and icosyl groups; cyclopropyl groups , cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group and other cyclic (alicyclic) alkyl groups. A part of the hydrogen atoms of the alkyl group may be substituted with an alkoxy group, an aryl group, a cyano group, a halogeno group, a hydroxyl group, a nitro group, or the like. The number of carbon atoms in the alkyl group (the number of carbon atoms excluding substituents) is preferably 1 to 20. Specifically, if the alkyl group is linear or branched, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5, and if it is a cyclic alkyl group, it preferably has 4 to 10 carbon atoms, more preferably 5 to 8 carbon atoms.

Aryl groups for R ^a1 include phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, and indenyl groups. A part of the hydrogen atoms of the aryl group may be substituted with an alkyl group, an alkoxy group, a cyano group, a halogeno group, a hydroxyl group, a nitro group, or the like. The number of carbon atoms in the aryl group (the number of carbon atoms excluding substituents) is preferably 6-20, more preferably 6-12.

The aralkyl group represented by R ^a1 includes benzyl, phenethyl, phenylpropyl, phenylbutyl, phenylpentyl, naphthylmethyl and the like. In the aryl group contained in the aralkyl group, part of the hydrogen atoms may be substituted with an alkyl group, an alkoxy group, a cyano group, a halogeno group, a hydroxyl group, a nitro group, or the like. The number of carbon atoms in the aralkyl group (the number of carbon atoms excluding substituents) is preferably 7-25, more preferably 7-15.

The amide groups of R ¹ and R ² are represented by the formula: *-C(=O)-NR ^a2 R ^a3 , where * represents the bonding site to the carbon atom of the ethylene double bond in formula (1). In the formula, R ^a2 represents a hydrogen atom or an alkyl group. R ^a3 represents a hydrocarbon group, preferably an alkyl group, acyl group, aryl group or aralkyl group. Specific examples of the alkyl group for R ^a2 and R ^a3 and the acyl group, aryl group and aralkyl group for R ^a3 are as described above for the alkyl group, aryl group and aralkyl group for R ^a1 and the acyl group for R ¹ and R ² . is referenced.

When both R ¹ and R ² are acyl groups, R ¹ and R ² may be linked ^together to form ^a ring. A group represented by *--C(=O)--R ^a4 --C(=O)-* is indicated. In the formula, R ^a4 represents a linear or branched alkylene group, and * represents the bonding site to the carbon atom of the ethylene double bond in formula (1). A part of the hydrogen atoms of the alkylene group may be substituted with an aryl group, an alkoxy group, a cyano group, a halogeno group, a hydroxyl group, a nitro group, or the like. The number of carbon atoms in the alkylene group of R ^a4 (the number of carbon atoms excluding substituents) is preferably 2-10, more preferably 3-8. Examples of the group (cyclic group) formed by linking the acyl groups of R ¹ and R ² include groups represented by the following formula (3-1).

When both R ¹ and R ² are carboxylic acid ester groups, R ¹ and R ² may be linked together to form a ring. In this case, the group formed by R ¹ and R ² is A group represented by the formula: *-C(=O)-OR ^a5 -OC(=O)-* is shown. In the formula, R ^a5 represents a linear or branched alkylene group, and * represents the bonding site to the carbon atom of the ethylene double bond in formula (1). A part of the hydrogen atoms of the alkylene group may be substituted with an aryl group, an alkoxy group, a cyano group, a halogeno group, a hydroxyl group, a nitro group, or the like. The number of carbon atoms in the alkylene group of R ^a5 (the number of carbon atoms excluding substituents) is preferably 1-8, more preferably 1-6. Examples of the group (cyclic group) formed by linking the carboxylic acid ester groups of R ¹ and R ² include groups represented by the following formula (3-2).

When both R ¹ and R ² are amide groups, R ¹ and R ² may be linked ^together to form ^a ring. A group represented by *-C(=O)-NR ^a6 -R ^a7 -NR ^a8 -C(=O)-* is indicated. In the formula, R ^a6 and R ^a8 represent a hydrogen atom or a hydrocarbon group, R ^a7 represents a linear or branched alkylene group or a carbonyl group, * represents the ethylene double bond of formula (1) represents the binding site to the carbon atom of The hydrocarbon groups of R ^a6 and R ^a8 are preferably alkyl groups, aryl groups or aralkyl groups. For specific examples of the alkyl group, aryl group and aralkyl group of R ^a6 and R ^a8 , the above description of the alkyl group, aryl group and aralkyl group of R ^a1 can be referred to. A part of the hydrogen atoms in the alkylene group of R ^a7 may be substituted with an aryl group, an alkoxy group, a cyano group, a halogeno group, a hydroxyl group, a nitro group, or the like. The number of carbon atoms in the alkylene group of R ^a7 (the number of carbon atoms excluding substituents) is preferably 1-8, more preferably 1-6. Examples of the group (cyclic group) formed by connecting the amide groups of R ¹ and R ² to each other include groups represented by the following formulas (3-3) and (3-4).

The hydrocarbon group for R ² includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group (aryl group). The aliphatic hydrocarbon group may be either saturated or unsaturated, and may be linear, branched or cyclic. For specific examples of the saturated aliphatic hydrocarbon group, see the above ^{description of the alkyl group for R a1 ,} and for specific examples of the unsaturated aliphatic hydrocarbon group, the carbon-carbon single Examples thereof include those in which a part of the bond is replaced with a double bond or a triple bond. For specific examples of the aromatic hydrocarbon group (aryl group), the above description of the aryl group for R ^a1 is referred to.

The heteroaryl group for ^R2 includes thienyl, thiopyranyl, isothiochromenyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyraridinyl, pyrimidinyl, pyridazinyl, thiazolyl, isothiazolyl, furanyl, A pyranyl group etc. are mentioned. In the heteroaryl group, the carbon atom is preferably bonded to the carbon atom of the ethylene double bond of formula (1), and the carbon atom adjacent to the hetero atom is the carbon atom of the ethylene double bond of formula (1) is more preferable, which facilitates the synthesis of the styrenic compound of formula (1). The number of carbon atoms in the heteroaryl group is preferably 3-18, more preferably 4-12.

In formula (1), R ² is preferably a hydrogen atom, a cyano group, an acyl group, a carboxylic acid ester group, or an amide group, which facilitates effective absorption of light in the ultraviolet to violet region. When it is desired to set the absorption peak on the longer wavelength side, for example, when it is desired to absorb light in the wavelength region of 350 nm to 420 nm instead of the complete ultraviolet region, R ² is preferably not a hydrogen atom.

R ³ in formula (1) represents a hydrogen atom or an alkyl group, and for specific examples of the alkyl group, refer to the above description of the alkyl group for R ^a1 . The alkyl group for R ³ preferably has 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms. A hydrogen atom is particularly preferred as R ³ .

In formula (1), the benzene ring bonded to the ethylene structure functions to donate electrons to the ethylene structure together with X (sulfur atom or oxygen atom) bonded to the benzene ring, and the chromophore of the ethylene structure Adjust the absorption wavelength of to be in the ultraviolet to violet region. R ⁴ bound to the benzene ring represents a hydrogen atom, an organic group or a polar functional group, and multiple R ^4s may be the same or different.

The organic group represented by R ⁴ in formula (1) includes an alkyl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an aralkyl group, an aryloxy group, an arylthio group, and an aryloxycarbonyl group. group, arylsulfonyl group, arylsulfinyl group, heteroaryl group, amino group, amide group, sulfonamide group, carboxy group (carboxylic acid group), cyano group and the like. The polar functional group of R ⁴ includes halogeno group, hydroxyl group, nitro group, sulfo group (sulfonic acid group) and the like.

For specific examples of the alkyl group for R ⁴ , the above description of the alkyl group for R ^a1 is referred to. The alkyl group of R ⁴ may have a substituent, and the substituents of the alkyl group include an aryl group, a heteroaryl group, a halogeno group, a hydroxyl group, a carboxy group, an alkoxy group, a cyano group, a nitro group, An amino group, a sulfo group, and the like can be mentioned.

For specific examples of the alkyl group included in the alkoxy group, alkylthio group, alkoxycarbonyl group, alkylsulfonyl group, and alkylsulfinyl group of R ⁴ , the description of the alkyl group of R ⁴ can be referred to.

For specific examples of the aryl group and aralkyl group for R ⁴ , the above description of the aryl group and aralkyl group for R ^a1 can be referred to. The aryl group contained in the aryl group or aralkyl group of R ⁴ may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a heteroaryl group, a halogeno group, a halogenoalkyl group, a hydroxyl group, a cyano group, nitro group, amino group, thiocyanate group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group and the like. be done.

For specific examples of the aryl group included in the aryloxy group, arylthio group, aryloxycarbonyl group, arylsulfonyl group, and arylsulfinyl group of R ⁴ , the description of the aryl group of R ⁴ can be referred to.

For specific examples of the heteroaryl group for R ⁴ , the description of the heteroaryl group for R ² above is referred to. The heteroaryl group may have a substituent, and the substituents that the heteroaryl group has include an alkyl group, an alkoxy group, an aryl group, a halogeno group, a halogenoalkyl group, a hydroxyl group, a cyano group, an amino group, and a nitro group. , thiocyanate group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group and the like.

The amino group for R ⁴ is represented by the formula: —NR ^a9 R ^a10 , where R ^a9 and R ^a10 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, or a heteroaryl and the like. Specific examples of the alkyl group, aryl group, aralkyl group, and heteroaryl group are described above, and as the alkenyl group and alkynyl group, part of the carbon-carbon single bond of the alkyl group described above is a double bond. Alternatively, substituents substituted for triple bonds may be mentioned, and in these substituents, part of the hydrogen atoms may be substituted with halogen atoms. Moreover, R ^a9 and R ^a10 may be linked to each other to form a ring.

Amido groups for R ⁴ include those represented by the formula: -NH-C(=O)-R ^a11 , where R ^a11 is an alkyl group, an aryl group, an aralkyl group or a heteroaryl group. Specific examples of the alkyl group, aryl group, aralkyl group, and heteroaryl group are described above, and part of the hydrogen atoms may be substituted with halogen atoms.

Examples of the sulfonamide group for R ⁴ include those represented by the formula: --NH--SO ₂ --R ^a12 , where R ^a12 is an alkyl group, an aryl group, an aralkyl group or a heteroaryl group. Specific examples of the alkyl group, aryl group, aralkyl group, and heteroaryl group are described above, and part of the hydrogen atoms may be substituted with halogen atoms.

The halogeno group for R ⁴ includes a fluoro group, a chloro group, a bromo group, an iodo group and the like.

R ⁴ is preferably one or more selected from a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aralkyl group, an aryloxy group and an arylthio group. For example, when R ⁴ is a nitrogen-containing substituent, the substituent R ⁴ decomposes or changes to another structure by heating or reaction, and the styrene compound tends to exhibit yellow or other coloring, which is less preferred. do not have. From the viewpoint of allowing the styrene compound to stably absorb light in the ultraviolet to violet region, R ⁴ is preferably a hydrogen atom or an alkyl group, and the alkyl group preferably has 1 to 4 carbon atoms. ~3 is more preferred. Among the four ^R4 's bonded to the benzene ring of the styrene compound, two or more are preferably hydrogen atoms, more preferably three or more are hydrogen atoms, and all four are hydrogen atoms. is particularly preferred.

Examples of the organic group for R ⁵ in formula (1) include an alkyl group, an aryl group, an aralkyl group, and a heteroaryl group. For specific examples of each of these groups, reference is made to the above description of the alkyl group, aryl group, aralkyl group, and heteroaryl group for R ⁴ . A part of the alkylene group contained in the alkyl group and the aralkyl group may be replaced with an ether bond (--O--) or a thioether bond (--S--) unless the position is adjacent to X.

X in formula (1) represents a sulfur atom or an oxygen atom, which stabilizes the styrene compound and facilitates absorption of light in the ultraviolet to violet region. From the viewpoint of effectively absorbing light in the UVA region, X is preferably a sulfur atom.

In the styrenic compound of formula (1), X may be bonded at the ortho-position, meta-position, or para-position with respect to the ethylene structure. From the viewpoint of ease of production of the styrenic compound, X is preferably bonded to the ethylene structure at the para-position.

As the styrene compound described above, it is preferable to use a compound represented by the following formula (2). The styrenic compound represented by the following formula (2) can enhance the adhesion of the resin layer to the substrate and has excellent heat resistance. Therefore, if the resin composition contains a styrene-based compound represented by the following formula (2) as the component (C), it will form a cured resin product with excellent adhesion to the substrate and excellent heat resistance. be able to. Since the resin composition of the present invention contains a thermoplastic resin as component (A), if it contains a styrene compound represented by the following formula (2) as component (C), the resin composition Even when the is heat-molded, the effect of the component (C) can be favorably exhibited. In particular, resins that require a thermosetting reaction at high temperatures (e.g., polyimide precursors, acrylic resins, etc.) and resins that require drying at high temperatures (e.g., resins containing high boiling point solvents and resins with high glass transition temperatures) Even when using, the effect of the component (C) can be preferably exhibited.

In formula (2), R ¹ to R ⁴ and X have the same meaning as above, a represents an integer of 2 or more, L represents a divalent or higher linking group, and the groups bonded to L are the same or can be different. The valence of a and the linking group L is preferably 8 or less, more preferably 6 or less, and even more preferably 4 or less. From the viewpoint that a highly stable styrenic compound can be easily produced, a is more preferably 3 or less, and particularly preferably 2.

The linking group L includes divalent linking groups such as an alkylene group, an arylene group, a heteroarylene group, -O-, -CO-, -S-, -SO-, _-SO2- , and -NH-; an alkyl group. trivalent linking groups such as a methine group (-C<) and -N<, which may have a; tetravalent linking groups such as >C<; and linking groups combining these. The alkylene group may be linear, branched, or cyclic. Moreover, the alkylene group and the arylene group may have a hydroxyl group and/or a thiol group. The linking groups --O--, --CO--, --S--, --SO--, --SO ₂ --, --NH-- and --N< are not provided adjacent to X.

From the viewpoint of enhancing the stability of the styrenic compound, the linking group L is an alkylene group in which some of the hydrogen atoms may be replaced with hydroxyl groups and/or thiol groups, and some of the hydrogen atoms are hydroxyl groups and/or thiols. An arylene group optionally substituted with a group, —O—, —S—, and a linking group combining these groups are preferred (wherein the ether bond and the thioether bond are not continuous and are provided adjacent to X do not have). The number of carbon atoms (the number of consecutive carbon atoms) in the linear or branched alkylene group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. If it is a cyclic alkylene group, the number of carbon atoms is preferably 4 or more, more preferably 5 or more, preferably 10 or less, and more preferably 8 or less. The number of carbon atoms in the arylene group is preferably 5 or more, more preferably 6 or more, and preferably 10 or less, more preferably 8 or less.

As the styrene compound, a styrene compound represented by the following formula (2-1) is particularly preferred. Such a styrenic compound has, for example, a peak with an absorption maximum in the wavelength range of 300 nm to 420 nm, and can effectively absorb light in the ultraviolet (UVA) to violet region, and has excellent stability. becomes easier. In the following formula (2-1), the description of R ^1a and R ^1b is referred to the description of R ¹ above, the description of R ^2a and R ^2b is referred to the description of R ² above, and R ^3a and R ^3b are referred to. The description of R3 is referred to above ^, and the description of ^{Xa and Xb is} referred to the description of X above.

The number of styrene compounds used as component (C) may be one, or two or more. In addition to UV absorbers (especially styrene compounds) that can be used as component (C), the resin composition contains other UV absorbers (e.g., benzotriazole compounds, benzophenone compounds, salicylic acid compounds, benzoxazinone compound, cyanoacrylate-based compound, benzoxazole-based compound, merocyanine-based compound, triazine-based compound, etc.).

The content of component (C) in the resin composition is preferably 0.01% by mass or more based on 100% by mass of the solid content of the resin composition, from the viewpoint of expressing desired performance, and 0.03% by mass. % or more is more preferable, and 0.1% by mass or more is even more preferable. Further, from the viewpoint of improving the moldability and film-forming properties of the resin composition, the content of the component (C) in the resin composition is preferably 25% by mass or less based on 100% by mass of the solid content of the resin composition. 20% by mass or less is more preferable, and 15% by mass or less is even more preferable. When the resin composition contains a styrenic compound as the component (C), the content of the styrenic compound is also preferably within the above range. When the resin composition also contains other ultraviolet absorbers, the total content thereof is preferably within the above range. The content of the other ultraviolet absorber is preferably 100 parts by mass or less, more preferably 60 parts by mass or less, and 30 parts by mass or less with respect to 100 parts by mass of the ultraviolet absorber used as component (C). is more preferred.

The resin composition may further contain a near-infrared absorbing colorant and/or a visible light absorbing colorant as component (D). If the resin composition further contains a near-infrared absorbing dye and/or a visible light absorbing dye as component (D), an optical filter having selective light transmission properties can be obtained from the resin composition. For example, if the resin composition contains a near-infrared absorbing dye as the component (D), the transmission of light in the ultraviolet to violet region and the red to near-infrared region is suppressed, and light in the visible region is preferentially transmitted. It can be a resin composition for a light selective transmission filter that allows transmission. When the resin composition contains a visible light absorbing colorant as the component (D), it can be used as a resin composition for colored filters, blue light reduction filters, and the like.

The near-infrared absorbing dye preferably has an absorption maximum in the wavelength range of 680 nm or more and 1100 nm or less. The near-infrared absorbing dye more preferably has a peak having an absorption maximum in a wavelength range of 680 nm or more and 1100 nm or less in an absorption spectrum in a wavelength range of 450 nm or more and 1100 nm or less, and the absorption maximum of the absorption peak is at a wavelength of 450 nm. It takes the maximum value in the range of 1100 nm or less. The absorption maximum wavelength is more preferably 685 nm or longer, more preferably 690 nm or longer, more preferably 1000 nm or shorter, still more preferably 900 nm or shorter, and even more preferably 800 nm or shorter.

As the visible light absorbing dye, any dye can be used without particular limitation as long as it has maximum absorption in the visible light region (for example, the wavelength range of more than 420 nm and less than 680 nm). Among them, as the visible light absorbing dye, it is preferable to use a dye having a maximum absorption in a wavelength range of 500 nm or more and less than 680 nm, which has high visibility.

The near-infrared absorbing dye and the visible light absorbing dye may be organic dyes, inorganic dyes, or organic-inorganic composite dyes (for example, organic compounds in which metal atoms or ions are coordinated). Not limited. Examples of near-infrared absorbing dyes and visible light absorbing dyes include squarylium-based dyes, croconium-based dyes, and copper (e.g., Cu(II)) or zinc (e.g., Zn(II)) as central metal ions. cyclic tetrapyrrole dyes (porphyrins, chlorins, phthalocyanines, naphthalocyanines, cholines, etc.), cyanine dyes, azo dyes, quinone dyes, xanthene dyes, indoline dyes, arylmethanes dyes, quaterrylene dyes, diimonium dyes, perylene dyes, quinacdrine dyes, oxazine dyes, dipyrromethene dyes, nickel complex dyes, copper ion dyes, and the like. Only one type of these dyes may be used, or two or more types may be used.

The content of component (D) in the resin composition is preferably 0.01% by mass or more based on 100% by mass of the solid content of the resin composition, from the viewpoint of expressing the desired performance, and 0.03% by mass. % or more is more preferable, and 0.1% by mass or more is even more preferable. Further, from the viewpoint of improving the moldability and film-forming properties of the resin composition, the content of the component (D) in the resin composition is preferably 25% by mass or less based on 100% by mass of the solid content of the resin composition. 20% by mass or less is more preferable, and 15% by mass or less is even more preferable. In addition, the total content of component (C) and component (D) (or the total content of other ultraviolet absorbers combined) is 30% by mass or less in 100% by mass of the solid content of the resin composition. is preferred, 25% by mass or less is more preferred, and 20% by mass or less is even more preferred.

When the resin composition is used as a resin composition for a light selective transmission filter that preferentially transmits light in the visible light region, a squarylium-based dye or a croconium-based dye can be used as the near-infrared absorbing dye. preferable. When such dyes are used, squarylium-based dyes and croconium-based dyes can be obtained by using epoxy group-containing silane coupling agents as component (B) silane coupling agents (including hydrolysates and hydrolyzed condensates). It is also possible to obtain the effect of improving the durability of

As the squarylium-based dye, for example, a squarylium compound represented by the following formula (6) can be used, and as the croconium-based dye, it is preferable to use, for example, a croconium compound represented by the following formula (7). In formulas (6) and (7) below, R ²¹ to R ²⁴ each independently represent a group represented by formula (8) or (9) below. A squarylium compound or croconium compound having a group represented by the following formula (8) has a broad absorption peak in the red to near-infrared region, and can cut light in a relatively wide wavelength range. On the other hand, a squarylium compound or croconium compound having a group represented by the following formula (9) has a sharp absorption peak in the red to near-infrared region, so light in a wavelength region corresponding to this absorption peak is selected. It is possible to cut it effectively.

In formula (8), ring P represents an optionally substituted aromatic hydrocarbon ring, aromatic heterocyclic ring, or condensed ring containing these ring structures, and R ³¹ to R ³³ are each independently represents a hydrogen atom, an organic group or a polar functional group, and R ³² and R ³³ may be linked together to form a ring. In formula (9), R ³⁴ to R ³⁸ each independently represent a hydrogen atom, an organic group or a polar functional group, R ³⁴ and R ³⁵ , R ³⁵ and R ³⁶ , R ³⁶ and R ³⁷ , R ³⁷ and Each R ³⁸ may be linked to each other to form a ring. * represents a binding site to the 4-membered ring in formula (6) or the 5-membered ring in formula (7).

The squarylium compound and the croconium compound may have a compound in a resonance relationship, but the squarylium compound represented by the above formula (6) and the croconium compound represented by the above formula (7) Compounds in these resonance relationships are also included.

For details of the organic groups and polar functional groups of R ³¹ to R ³⁸ , refer to the description of the organic group and polar functional group of R ⁴ above. When R ³¹ to R ³⁸ are independent groups, each of R ³¹ to R ³⁸ is preferably a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an amino group, an amido group or a hydroxy group. For details of these groups, reference is made to the description of R ⁴ above.

Each ring structure formed from R ³² to R ³⁸ includes a hydrocarbon ring and a heterocyclic ring, and these ring structures may or may not have aromaticity. A hydrocarbon ring or a non-aromatic heterocyclic ring is preferred. Non-aromatic hydrocarbon rings include, for example, cycloalkanes such as cyclopentane, cyclohexane and cycloheptane; are mentioned. As the non-aromatic heterocyclic ring, one or more carbon atoms constituting the hydrocarbon ring as described above are selected from N (nitrogen atom), S (sulfur atom) and O (oxygen atom). Rings in which at least one or more atoms are substituted are included. Non-aromatic heterocycles include, for example, pyrrolidine ring, tetrahydrofuran ring, tetrahydrothiophene ring, piperidine ring, tetrahydropyran ring, tetrahydrothiopyran ring, morpholine ring, hexamethyleneimine ring, hexamethylene oxide ring, hexamethylene sulfide ring, A heptamethyleneimine ring and the like are included.

In the group of formula (8), the ring structure formed by linking R ³² and R ³³ is preferably a 4- to 9-membered unsaturated hydrocarbon ring, especially cyclopentene, cyclohexene, cycloheptene, cyclo Cycloalkanemonoenes such as octene are more preferred. If the group of formula (8) is constituted in this way, the shoulder peak of the absorption waveform in the red to near-infrared region is reduced, and the absorption peak becomes sharp.

Examples of the aromatic hydrocarbon ring of ring P in formula (8) include benzene ring, naphthalene ring, phenanthrene ring, anthracene ring, fluoranthene ring, cyclotetradecaheptaene ring and the like. The aromatic hydrocarbon ring may have only one ring structure, or two or more ring structures may be condensed. The aromatic heterocyclic ring of ring P contains one or more atoms selected from N (nitrogen atom), O (oxygen atom) and S (sulfur atom) in the ring structure and has aromaticity, for example , furan ring, thiophene ring, pyrrole ring, pyrazole ring, oxazole ring, thiazole ring, imidazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, purine ring, pteridine ring and the like. The aromatic heterocyclic ring may have only one ring structure, or may have two or more ring structures condensed. The condensed ring containing these ring structures of the ring P has a structure in which an aromatic hydrocarbon ring and an aromatic heterocyclic ring are condensed, such as indole ring, isoindole ring, benzimidazole ring, quinoline ring , benzopyran ring, acridine ring, xanthene ring, carbazole ring and the like. By appropriately setting the π-conjugated system of the ring P, the absorption wavelength in the red to near-infrared region can be easily adjusted.

The ring P may have a substituent, and examples of the substituent include the above-described organic groups and polar functional groups. When the ring P has a substituent, the number thereof is preferably 1-3, more preferably 1-2, and still more preferably 1. Ring P may not have a substituent.

For details of the squarylium compound and croconium compound having the group of formula (8), refer to the description in JP-A-2016-74649.

In the group represented by formula (9), R ³⁵ and R ³⁶ are preferably linked to form a ring, and R ³⁶ and R ³⁷ may be linked to form a ring. In this case, at least R ³⁴ and R ³⁸ are independent groups. If the group of formula (9) is constituted in this way, the absorption peak in the red to near-infrared region will be sharp. The number of ring members of the ring structure formed from R ³⁵ and R ³⁶ and the ring structure formed from R ³⁶ and R ³⁷ is preferably 5 or more, more preferably 6 or more, preferably 12 or less, and more preferably 10 or less. Preferably, 8 or less is more preferable.

In the group represented by formula (9), R ³⁶ is an amino group, R ³⁶ which is an amino group is linked to R ³⁵ to form a ring, or is linked to R ³⁷ to form a ring preferably. In this case, the maximum absorption wavelength shifts to the long wavelength side (for example, 685 nm or more), the transmittance of light in the red region is increased, and the color of the transmitted light can be brought closer to the actual color. From the same point of view, R ³⁴ or R ³⁸ is preferably an amide group.

In the squarylium compound and croconium compound having a group represented by formula (9), the benzene rings on both sides of the squarylium skeleton or croconium skeleton may be connected by a connecting group. Examples of such compounds include squarylium compounds disclosed in JP-A-2015-176046.

The resin composition may contain a solvent. For example, when the resin composition is a resin composition that has been made into a paint, the inclusion of a solvent facilitates the coating of the resin composition. The solvent may function as a solvent (solvent) for components (A) to (C), or may function as a dispersion medium. Examples of solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; glycol derivatives such as PGMEA (2-acetoxy-1-methoxypropane), ethylene glycol monobutyl ether, ethylene glycol monoethyl ether and ethylene glycol ethyl ether acetate. (ether compounds, ester compounds, ether ester compounds, etc.); amides such as N,N-dimethylacetamide; esters such as ethyl acetate, propyl acetate, butyl acetate; N-methyl-pyrrolidone (specifically, 1 -methyl-2-pyrrolidone, etc.); aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as cyclohexane and heptane; ethers such as tetrahydrofuran, dioxane, diethyl ether and dibutyl ether; is mentioned. These solvents may be used alone or in combination of two or more.

The solvent content is, for example, preferably 50% by mass or more, more preferably 70% by mass or more, preferably less than 100% by mass, and more preferably 95% by mass or less in 100% by mass of the resin composition. By adjusting the content of the solvent within such a range, it becomes easy to obtain a resin composition having a high concentration of each component.

The resin composition may contain a surface modifier, which suppresses appearance defects such as striations and dents in the resin layer when the resin composition is cured to form a resin layer. can do. The type of the surface modifier is not particularly limited, and siloxane-based surfactants, acetylene glycol-based surfactants, fluorine-based surfactants, acrylic leveling agents, and the like can be used. As the surface conditioner, for example, the BYK (registered trademark) series manufactured by BYK Chemie, the KF series manufactured by Shin-Etsu Chemical Co., Ltd., or the like can be used.

The resin composition may contain a dispersant, which stabilizes the dispersibility of the resin composition and suppresses reaggregation. The type of dispersant is not particularly limited, and EFKA series manufactured by Efka Additives, BYK (registered trademark) series manufactured by BYK Chemie, Solsperse (registered trademark) series manufactured by Nippon Lubrizol, and Disparon manufactured by Kusumoto Kasei Co., Ltd. (registered trademark) series, Ajinomoto Fine Techno Co., Ltd. Ajisper (registered trademark) series, Shin-Etsu Chemical Co., Ltd. KP series, Kyoeisha Chemical Co., Ltd. Polyflow series, DIC Corporation Megafac (registered trademark) series, San Nopco's Disper Aid series or the like can be used.

The resin composition may contain various additives such as plasticizers, surfactants, viscosity modifiers, antifoaming agents, antiseptics, resistivity modifiers, adhesion improvers, etc., as necessary. .

The resin composition can be made into a cured product by curing. The resin composition can be made into a cured product by injection molding, extrusion molding, vacuum molding, compression molding, blow molding, or the like. In this case, the resin composition may be molded after heating to about 150° C. to 350° C. for melting. The shape of the molded article is not particularly limited, but may be plate-like, sheet-like, granular, powdery, lumpy, particle aggregate, spherical, ellipsoidal, lens-like, cubic, columnar, rod-like, cone-like, Cylindrical, acicular, fibrous, hollow fiber, porous and the like can be mentioned. Further, when kneading the resin, an additive such as a plasticizer, which is used in general resin molding, may be added.

The resin composition can be coated by spin coating, solvent casting, roll coating, spray coating, bar coating, dip coating, slit coating, screen printing, flexographic printing, ink jet, or the like. It may be a modified one. In this case, a liquid or paste resin composition is coated on a substrate (for example, a resin plate, a film, a glass plate, etc.) to form a film having a thickness of 200 μm or less or a sheet having a thickness of more than 200 μm. A cured product can be obtained. The cured product of the resin composition obtained in this manner can be handled in an integrated manner with the substrate. Since the resin composition of the present invention has excellent adhesion to a substrate, it is preferably handled as a resin composition that has been made into a paint.

INDUSTRIAL APPLICABILITY The resin composition of the present invention can be preferably used as a resin composition for forming filters used in various applications such as optical device applications, display device applications, mechanical parts, electric/electronic parts and the like. The resin composition can be used, for example, for optical filters such as UV cut filters and light selective transmission filters.

Imaging devices such as mobile phone cameras, digital cameras, in-vehicle cameras, video cameras, and display devices (such as LEDs) generally use imaging devices that convert light from a subject into electrical signals and output them. Such imaging devices are equipped with light-receiving devices such as CCDs (Charge Coupled Devices) and CMOSs (Complementary Metal-Oxide Semiconductors) and lenses. For example, a light selective transmission filter is provided to remove ghosts and flares. Such a light selective transmission filter is usually provided with a dielectric multilayer film in which high refractive index material layers and low refractive index material layers are alternately laminated. By adjusting the thickness of each layer of the low refractive index material layer, it is possible to cut off the incidence of light in a desired wavelength range.

However, since the cut wavelength range or transmission wavelength range of the dielectric multilayer film changes depending on the incident angle, the cut wavelength range or transmission wavelength range shifts to the short wavelength side when the incident angle changes from the vertical direction to the oblique direction. For this reason, the dielectric multilayer film may not be able to sufficiently cut light in the desired wavelength range for incident light in an oblique direction, or may cut light in the visible light range, resulting in a change in color. . In recent years, there has been a strong demand for image sensors to be both smaller and thinner. sex comes out. In this case, since the incident angle dependence of the cut wavelength region and the transmission wavelength region becomes stronger, light in the short wavelength region, that is, light in the ultraviolet to violet region, which had almost no effect in the past, shifts to the short wavelength side. It will become apparent.

Since the resin composition of the present invention contains an ultraviolet absorber as the component (C), an optical filter formed from the resin composition can selectively absorb light in the ultraviolet to violet region, and short wavelengths in the visible light region. It is possible to reduce the incident angle dependence on the side. If the resin composition also contains a near-infrared absorbing dye as the component (D), the optical filter formed from the resin composition has an incident angle of It can reduce dependence. When the compound represented by the above formula (2) is used as the ultraviolet absorber of component (C), the excellent heat resistance of the compound can be used when the resin composition is heat-molded, or when the dielectric multilayer is formed by vapor deposition. Even when a film is provided, decomposition and volatilization of the compound can be suppressed, and light in the ultraviolet to violet region can be effectively cut. Furthermore, even if the optical filter is exposed to ultraviolet light during storage, manufacturing, and processing (e.g. vapor deposition, mounting, etc.), deterioration of resin components and near-infrared absorbing pigments caused by the ultraviolet light can be suppressed. can.

As the optical filter, a resin layer obtained by curing the resin composition of the present invention is preferably formed on a substrate, whereby an optical filter in which the substrate and the resin layer are laminated and integrated with high adhesion can be obtained. The resin layer may be provided only on one surface of the substrate, or may be provided on both surfaces.

Although the thickness of the resin layer is not particularly limited, it is preferably 0.5 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more from the viewpoint of ensuring desired light selective transmission performance. The upper limit of the thickness of the resin layer may be, for example, 1 mm or less, 500 μm or less, 200 μm or less, or 50 μm or less. When a resin composition that has been made into a paint is applied onto a substrate by a spin coating method, the thickness of the resin layer can be formed even thinner, and from the viewpoint of forming a thinner optical filter, the resin layer has a thickness of 20 μm or less. is preferred, 10 µm or less is more preferred, and 5 µm or less is even more preferred.

As the substrate, it is preferable to use a transparent substrate such as a resin plate, a resin film, or a glass plate. Among them, it is preferable to use a glass substrate as the substrate. By providing the resin layer on the glass substrate, an optical filter having excellent heat resistance can be obtained. The optical filter thus obtained can be mounted on an electronic component by, for example, solder reflow, and the size of the electronic component can be reduced. In addition, since the glass substrate is less likely to crack or warp even when exposed to high temperatures, it becomes easier to secure adhesion to the resin layer. Furthermore, by using a glass substrate, it becomes easy to improve the adhesion between the resin layer and the glass substrate by the action of the component (B).

Known glasses such as silicate glass, borosilicate glass, borate glass, and phosphate glass can be used for the glass substrate. In these glasses, silicon atoms, boron atoms or phosphorus atoms form a network structure with oxygen atoms to form the main skeleton of the glass. In addition to these atoms, the glass contains sodium, potassium, calcium, Atoms or ions such as magnesium, barium, aluminum, iron, silver, copper, cobalt, nickel, lead, zinc, fluorine may be present. The glass may be colorless and transparent, or colored glass such as blue glass may be used depending on the application.

For example, the thickness of the substrate is preferably 0.05 mm or more, more preferably 0.1 mm or more, from the viewpoint of ensuring strength, and is preferably 0.4 mm or less, and more preferably 0.3 mm or less from the viewpoint of thinning. .

A protective layer made of the same or different resin as that of the resin layer may be laminated as a second resin layer on the resin layer formed from the resin composition of the present invention. By providing the protective layer, the durability (decomposition resistance) of each component contained in the resin layer can be enhanced. The protective layer may be provided only on one side of the resin layer, or may be provided on both sides.

The optical filter has an antireflection and antiglare layer (antireflection film) that reduces glare from fluorescent lights, etc., a layer that prevents scratches, and a transparent base material that has other functions. may The optical filter may have an ultraviolet reflecting film or a near-infrared reflecting film on the resin layer. It is preferable that the ultraviolet reflective film and the near-infrared reflective film are provided on the light incident side of the resin layer. If the optical filter is provided with an ultraviolet reflective film or a near-infrared reflective film, it is possible to cut more ultraviolet rays and near-infrared rays from the light transmitted through the optical filter. The ultraviolet reflective film and the near-infrared reflective film may be one having the ultraviolet reflective function and the near-infrared reflective function.

The ultraviolet reflective film, the near-infrared reflective film, and the antireflection film (visible light antireflection film) can be composed of a dielectric multilayer film in which high refractive index material layers and low refractive index material layers are alternately laminated. Therefore, when imparting such a function to an optical filter, the optical filter preferably has a dielectric multilayer film. A material having a refractive index of 1.7 or more can be used as a material constituting the high refractive index material layer, and a material having a refractive index ranging from 1.7 to 2.5 is usually selected. Examples of materials constituting the high refractive index material layer include oxides such as titanium oxide, zinc oxide, zirconium oxide, lanthanum oxide, yttrium oxide, indium oxide, niobium oxide, tantalum oxide, tin oxide, and bismuth oxide; silicon nitride; Nitrides such as; said oxides, mixtures of said nitrides, and those doped with metals such as aluminum and copper or carbon (for example, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO)), etc. be done. A material having a refractive index of 1.6 or less can be used as the material constituting the low refractive index material layer, and a material having a refractive index ranging from 1.2 to 1.6 is usually selected. Examples of materials forming the low refractive index material layer include silicon dioxide (silica), alumina, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride.

The optical filter may also have an aluminum deposition film, a noble metal thin film, a resin film in which metal oxide fine particles containing indium oxide as a main component and a small amount of tin oxide are dispersed, or the like.

The thickness of the optical filter is preferably 1 mm or less, for example. As a result, for example, it is possible to sufficiently meet the demand for miniaturization of the imaging device. The thickness of the optical filter is more preferably 500 μm or less, still more preferably 300 μm or less, still more preferably 150 μm or less, more preferably 30 μm or more, and even more preferably 50 μm or more.

An optical filter can be used as one of constituent members of sensors such as an image sensor (imaging device), an illuminance sensor, and a proximity sensor. For example, an image sensor is used as an electronic component that converts light from an object into an electrical signal or the like and outputs the signal. Image sensors can be used for mobile phone cameras, digital cameras, vehicle-mounted cameras, surveillance cameras, display elements (LEDs, etc.), and the like. The sensor includes one or more of the optical filters described above, and may optionally have other filters (eg, visible light cut filter, infrared cut filter, ultraviolet cut filter, etc.) and lenses.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples, and can be carried out with appropriate changes within the scope that can conform to the gist of the above and later descriptions. All of them are included in the technical scope of the present invention.

(1) Synthesis of compounds (1-1) Synthesis Example 1: Synthesis of UV absorber A In a 200 mL four-necked flask, 4.98 g (0.039 mol) of 4-fluorobenzaldehyde, ethylene glycol bis(2-mercaptoethyl) 3.57 g (0.020 mol) of ether, 10.86 g (0.079 mol) of potassium carbonate, and 74 g of acetonitrile were charged, and reacted at 60° C. for 12 hours under nitrogen flow (10 mL/min) while stirring using a stirring blade. rice field. After completion of the reaction, the insoluble matter was filtered off by filtration under reduced pressure, and the solvent was distilled off using an evaporator. The obtained concentrate was placed in a 200 mL four-necked flask, and 11.09 g (0.079 mol) of isobutyl cyanoacetate, 3.32 g (0.039 mol) of piperidine, and 68 g of methanol were added and reacted under reflux conditions for 4 hours. let me After completion of the reaction, the solvent was distilled off using an evaporator, and the resulting concentrate was purified by column chromatography (developing solvent: chloroform) to obtain UV absorber A shown in Table 1. When the transmission spectrum of UV absorber A in toluene was measured, the maximum absorption wavelength was 364 nm.

(1-2) Synthesis Example 2: Synthesis of UV Absorber B In Synthesis Example 1, except that malononitrile was used instead of isobutyl cyanoacetate, the same procedure as in Synthesis Example 1 was followed to obtain UV absorber B shown in Table 1. got When the transmission spectrum of UV absorber B in toluene was measured, the maximum absorption wavelength was 381 nm.

(1-3) Synthesis Example 3: Synthesis of UV Absorber C In Synthesis Example 1, except that dibutyl malonate was used instead of isobutyl cyanoacetate, the same procedure as in Synthesis Example 1 was performed to absorb ultraviolet rays shown in Table 1. Agent C was obtained. When the transmission spectrum of UV absorber C in toluene was measured, the maximum absorption wavelength was 325 nm.

(1-4) Synthesis Example 4: Synthesis of near-infrared absorbing dye A Near-infrared absorbing dye A (squarylium compound) shown in Table 1 according to the method described in Example 1-18 of JP-A-2016-74649. was synthesized. When the transmission spectrum of the near-infrared absorbing dye A in toluene was measured, the maximum absorption wavelength was 737 nm.

(1-5) Synthesis Example 5: Synthesis of near-infrared absorbing dye B In a 300 mL four-necked flask, 110 g of chloroform, 1.8 g of acetic acid, 5.4 g of 7-nitro-1,2,3,4-tetrahydroquinoline ( 0.0303 mol) and 12.84 g (0.0606 mol) of sodium triacetoxyborohydride are added, and 4.37 g (0.0606 mol) of isobutyraldehyde is added to the solution while stirring with a stirring blade under nitrogen flow (10 mL/min). It was added dropwise over a period of minutes. After completion of dropping, the obtained reaction liquid was added to 300 g of water and neutralized with hydrochloric acid. 300 g of ethyl acetate was added thereto, the organic phase was extracted with a separating funnel, and magnesium sulfate (anhydrous) was added to the extracted organic phase for dehydration. After filtering off solids (inorganic matter) from this organic phase, after concentrating the solvent using an evaporator, using silica gel column chromatography (developing solvent: chloroform) as appropriate, and concentrating and vacuum drying, 1 -isobutyl-7-nitro-1,2,3,4-tetrahydroquinoline.

Next, 2.8 g (0.012 mol) of 1-isobutyl-7-nitro-1,2,3,4-tetrahydroquinoline and 9.0 g of concentrated hydrochloric acid (hydrochloric acid concentration: 36% by weight) were added, and nitrogen flow (5 mL) was added. /min), while stirring with a magnetic stirrer, a solution containing 9.1 g of tin chloride dihydrate and 9.1 g of concentrated hydrochloric acid (concentration of hydrochloric acid: 36% by weight) was added a little while paying attention to the heat of reaction. added one by one. After the addition, the mixture was stirred at room temperature for about 3 hours. After that, the obtained reaction liquid was added to a beaker containing 100 g of pure water and 100 g of ethyl acetate while stirring. Potassium hydroxide solution was added little by little, and after stirring for a while when the pH of the aqueous solution reached around 10, the organic phase was extracted with a separating funnel, and magnesium sulfate (anhydrous) was added to the extracted organic phase. dehydrated. After filtering off solids (inorganic matter) from this organic phase, after concentrating the solvent using an evaporator, using silica gel column chromatography (developing solvent: chloroform) as appropriate, and concentrating and vacuum drying, 1 -isobutyl-7-amino-1,2,3,4-tetrahydroquinoline.

Next, 2.86 g (0.0143 mol) of 1-isobutyl-7-amino-1,2,3,4-tetrahydroquinoline and 50 g of superdehydrated chloroform are placed in a 100 mL three-necked flask, and nitrogen is passed through (5 mL/ min), while stirring with a magnetic stirrer, 4.34 g (0.0429 mol) of triethylamine and 7.86 g (0.0286 mol) of palmitoyl chloride (n-hexadecanoyl chloride) were added, and the mixture was stirred at room temperature for 12 hours. reacted. After completion of the reaction, the resulting reaction solution was added to ion-exchanged water and extracted with ethyl acetate. Magnesium sulfate (anhydrous) was added to the extracted organic phase for dehydration. After filtering off solids (inorganic matter) from this organic phase, after concentrating the solvent using an evaporator, using silica gel column chromatography (developing solvent: chloroform) as appropriate, and concentrating and vacuum drying, 1 -isobutyl-7-(N-palmitoylamino)-1,2,3,4-tetrahydroquinoline.

Next, 6.3 g (0.0143 mol) of 1-isobutyl-7-(N-palmitoylamino)-1,2,3,4-tetrahydroquinoline and 0.82 g (0.0143 mol) of squaric acid were placed in a 300 mL two-necked flask. 0072 mmol), 30 g of 1-butanol, and 30 g of toluene are added, stirred with a magnetic stirrer under nitrogen flow (10 mL/min), and are brought to reflux conditions while removing eluted water using a Dean-Stark apparatus. and reacted for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitate was separated by filtration. The precipitate separated by filtration was washed with methanol, and only the precipitate was filtered again, and the resulting cake (solid matter) was purified by column chromatography (developing solvent: chloroform) using alumina. The obtained purified product was dried at 60° C. for 12 hours using a vacuum dryer to obtain a near-infrared absorbing dye B (squarylium compound) shown in Table 1. When the transmission spectrum of the near-infrared absorbing dye B in toluene was measured, the maximum absorption wavelength was 700 nm.

(1-6) Synthesis Example 6: Synthesis of Visible Light Absorbing Dye A
According to the procedure described in Tetrahedron Letters, Vol.40, pp.4067-4068 (1999), visible light absorbing dye A shown in Table 1 was synthesized. When the transmission spectrum of visible light absorbing dye A in chloroform was measured, the maximum absorption wavelength was 655 nm.

(2) Preparation of Resin Composition (2-1) Preparation Example 1: Preparation of Resin Composition 1 Into a 2-liter reaction vessel equipped with a stirring blade, 2,2'-bis(4-hydroxyphenyl)propane 10 was added. 0.01 g (0.044 mol), 3.59 g (0.090 mol) of sodium hydroxide, and 300 g of ion-exchanged water were charged and dissolved, and then 0.89 g (0.009 mol) of triethylamine was added and dissolved. A solution prepared by dissolving 3.57 g (0.021 mol) of terephthalic acid dichloride and 3.57 g (0.021 mol) of isophthalic acid dichloride in 500 g of methylene chloride was placed in a dropping funnel and attached to the reaction vessel. The solution in the reaction vessel was stirred while being kept at 20° C., and the methylene chloride solution was added dropwise from the dropping funnel over 60 minutes. Further, a solution of 0.71 g (0.005 mol) of benzoyl chloride dissolved in 10 g of methylene chloride was added thereto and stirred for 60 minutes. An acetic acid aqueous solution was added to the obtained reaction solution to neutralize it, and after adjusting the pH of the aqueous phase to 7, the oil phase and the aqueous phase were separated using a separating funnel. The obtained oil phase was added dropwise to methanol with stirring to reprecipitate the polymer, and the precipitate was collected by filtration and dried in an oven at 80° C. to obtain a white solid polyarylate resin (PAR resin). The obtained polyarylate resin had a polystyrene-equivalent weight average molecular weight (Mw) of 33,780 and a number average molecular weight (Mn) of 8,130 as measured by gel permeation chromatography.

Add 9.9 parts by mass of the polyarylate resin obtained above to a mixed solvent of 43.5 parts by mass of toluene and 43.5 parts by mass of o-xylene, and further add 1.1 parts by mass of UV absorber A there. 0.8 parts by mass of infrared absorbing dye A, 0.3 parts by mass of near-infrared absorbing dye B, and 0.03 parts by mass of BYK-310 (polyether-modified polydimethylsiloxane) manufactured by BYK Chemie as a surface conditioner. , mixed uniformly. The base resin composition thus obtained was combined with a mercapto group-containing silane coupling agent (X-12-1154, manufactured by Shin-Etsu Silicone Co., Ltd.) at a mass ratio of base resin composition: silane coupling agent = 99: 1. The resin composition 1 was obtained by uniformly mixing at 25° C. and filtering this through a filter with a pore size of 0.1 μm (manufactured by GL Sciences, non-aqueous 13N) to remove foreign matter.

(2-2) Preparation Example 2: Preparation of Resin Composition 2 In Preparation Example 1, an amino group-containing silane coupling agent (manufactured by Shin-Etsu Silicone Co., Ltd., KBP-90) was used instead of the mercapto group-containing silane coupling agent. A resin composition 2 was obtained in the same manner as in Preparation Example 1 except for the above.

(2-3) Preparation Example 3: Preparation of Resin Composition 3 In Preparation Example 1, instead of the mercapto group-containing silane coupling agent, an alkylene glycol group (—CH(OH)CH ₂ OH)-containing silane coupling agent (Shin-Etsu Resin composition 3 was obtained in the same manner as in Preparation Example 1, except that X-12-1098 manufactured by Silicone Co., Ltd. was used.

(2-4) Preparation Example 4: Preparation of Resin Composition 4 In Preparation Example 1, a carboxyl group-containing silane coupling agent (manufactured by Shin-Etsu Silicone Co., Ltd., X-12-1135) was used instead of the mercapto group-containing silane coupling agent. A resin composition 4 was obtained in the same manner as in Preparation Example 1, except that it was used.

(2-5) Preparation Example 5: Preparation of Resin Composition 5 In Preparation Example 1, instead of the mercapto group-containing silane coupling agent, an epoxy group-containing silane coupling agent (manufactured by Shin-Etsu Silicone Co., Ltd., X-12-981S; polymer A resin composition 5 was obtained in the same manner as in Preparation Example 1, except that a polyfunctional epoxy group-containing silane coupling agent) was used.

(2-6) Preparation Example 6: Preparation of Resin Composition 6 In Preparation Example 1, instead of the mercapto group-containing silane coupling agent, an epoxy group-containing silane coupling agent (manufactured by Dow Corning Toray Co., OFS-6040; 3 -Glycidoxypropyltrimethoxysilane) was used in the same manner as in Preparation Example 1 to obtain a resin composition 6.

(2-7) Preparation Example 7: Preparation of Resin Composition 7 Preparation Example 1 except that a hydrolyzed solution of an epoxy group-containing silane coupling agent was used instead of the mercapto group-containing silane coupling agent in Preparation Example 1. Resin composition 7 was obtained in the same manner as above. The compounding ratio of the polyarylate resin composition and the hydrolyzed solution of the epoxy group-containing silane coupling agent was the former:the latter=99:1 (mass ratio). The hydrolysis solution of the epoxy group-containing silane coupling agent includes 24.7 parts by mass of 3-glycidoxypropyltrimethoxysilane (OFS-6040 manufactured by Dow Corning Toray Co., Ltd.) and 32.1 parts by mass of 2-propanol. and 3.4 parts by mass of distilled water were blended and uniformly mixed at 25° C., then 1.54 parts by mass of formic acid was added and mixed for 90 minutes to initiate the hydrolysis reaction of 3-glycidoxypropyltrimethoxysilane. Prepared by proceeding.

(2-8) Preparation Example 8: Preparation of Resin Composition 8 In Preparation Example 7, except that the amount of UV absorber A mixed in the polyarylate resin was changed from 1.1 parts by mass to 0.55 parts by mass, A resin composition 8 was obtained in the same manner as in Preparation Example 7.

(2-9) Preparation Example 9: Preparation of Resin Composition 9 Preparation Example 7, except that the near-infrared absorbing dye A and the near-infrared absorbing dye B were not blended into the polyarylate resin. A resin composition 9 was obtained in the same manner.

(2-10) Preparation Example 10: Preparation of Resin Composition 10 In Preparation Example 7, the same as Preparation Example 7, except that the ultraviolet absorber blended in the polyarylate resin was changed from ultraviolet absorber A to ultraviolet absorber B. Then, a resin composition 10 was obtained.

(2-11) Preparation Example 11: Preparation of Resin Composition 11 In Preparation Example 7, the same as Preparation Example 7, except that the ultraviolet absorber blended in the polyarylate resin was changed from ultraviolet absorber A to ultraviolet absorber C. Then, a resin composition 11 was obtained.

(2-12) Preparation Example 12: Preparation of Resin Composition 12 In Preparation Example 7, the dyes blended in the polyarylate resin were changed from near-infrared absorbing dye A and near-infrared absorbing dye B to visible light absorbing dye A, A resin composition 12 was obtained in the same manner as in Preparation Example 7, except that the ultraviolet absorbent was changed from the ultraviolet absorbent A to the ultraviolet absorbent C.

(2-13) Preparation Example 13: Preparation of Resin Composition 13 Resin composition 13 was obtained in the same manner as in Preparation Example 1, except that the silane coupling agent was not added to the polyarylate resin. rice field.

(2-14) Preparation Example 14: Preparation of Resin Composition 14 Resin composition 14 was obtained in the same manner as in Preparation Example 7, except that the ultraviolet absorber A was not added to the polyarylate resin. rice field.

(2-15) Preparation Example 15: Preparation of Resin Composition 15 A resin composition 15 was obtained in the same manner as in Preparation Example 7.

(3) Preparation of resin layer laminated substrate 2 cc of each resin composition obtained above was dripped onto a glass substrate (manufactured by Schott, D263Teco), and then using a spin coater (manufactured by Mikasa, 1H-D7), The rotation speed was increased to 1600 rotations over 0.2 seconds, held at that rotation speed for 20 seconds, and then reduced to 0 rotations over 0.2 seconds to form a film of the resin composition on the glass substrate. The glass substrate on which the resin composition was formed was replaced with nitrogen at 50° C. for 30 minutes using an inert oven (DN610I, manufactured by Yamato Kagaku Co., Ltd.), then heated to 190° C. in about 15 minutes, and heated to 190° C. in a nitrogen atmosphere. C. for 30 minutes to form a resin layer on the glass substrate (hereinafter referred to as "resin layer laminated substrate"). The thickness of the resin layer formed on the glass substrate was 2 μm. The thickness of the resin layer was obtained from the difference between the thickness of the glass substrate on which the resin layer was formed and the thickness of the glass substrate alone, which were each measured with a micrometer.

(4) Adhesion evaluation method (4-1) Initial peeling resistance test The resin layer of the resin layer laminated substrate obtained above is cut with a cutter (manufactured by NT Corporation, A-300), and cuts are made in columns and rows. 81 squares of 4 mm ² were prepared by providing 10 cross-cut lines at intervals of 2 mm to prepare a sample substrate for evaluation. A tape (Scotch (registered trademark) Transparent Adhesive Tape Transparent Bishoku (registered trademark) manufactured by 3M) was attached to the sample substrate to prevent air from entering, and the sample substrate was left for 5 seconds. Thereafter, the tape was peeled off from the sample substrate within 1 second and evaluated according to the following criteria. In addition, the tape was peeled off so that the peeling force was constant in any mass.

A: Of the 81 squares prepared, no peeling occurred B: Of the 81 squares prepared, peeling occurred in 1 to 9 squares C: Of the 81 squares prepared , Peeling occurred in squares 10 to 81 (4-2) Peeling resistance test after boiling in water The resin layer of the resin layer laminated substrate obtained above was cut with a cutter (manufactured by NT Corporation, A-300), 81 squares of 4 mm ² were prepared by providing 10 cross-cut lines at intervals of 2 mm in each of columns and rows to prepare a sample substrate for evaluation. Next, this sample substrate was placed in ultrapure water heated to a boiling state and boiled for 2 hours. Subsequently, at room temperature, a tape (Scotch (registered trademark) Transparent Adhesive Tape Transparent Bishoku (registered trademark) manufactured by 3M) was attached to prevent air from entering, and left for 5 seconds. Thereafter, the tape was peeled off from the sample substrate within 1 second and evaluated according to the following criteria. In addition, the tape was peeled off so that the peeling force was constant in any mass.

A: Of the 81 squares prepared, no peeling occurred B: Of the 81 squares prepared, peeling occurred in 1 to 9 squares C: Of the 81 squares prepared , Peeling occurred in 10 to 81 squares

(5) Results Table 2 shows the components of Resin Compositions 1 to 15 and the results of the adhesion evaluation test. Resin compositions 5 to 12 and 15 containing an epoxy group-containing silane coupling agent or a hydrolyzate (condensation) product thereof as component (B) and an ultraviolet absorber as component (C) were evaluated for adhesion after boiling in water. It was evaluated as A or B, and the initial adhesion was also evaluated as A. In particular, resin compositions 7, 9 to 12, and 15 containing a hydrolyzate (condensation) product of an epoxy group-containing silane coupling agent as component (B) were evaluated as A in adhesion after boiling in water. On the other hand, resin compositions 1 to 4 containing a silane coupling agent having a functional group other than an epoxy group, a resin composition 13 containing no silane coupling agent itself, and a resin composition containing no UV absorber as component (C). Regardless of the evaluation of the initial adhesion, all of the products 14 were evaluated as C in the adhesion evaluation after boiling in water. Resin layers formed from resin compositions 5 to 12 and 15 containing an epoxy group-containing silane coupling agent or a hydrolyzate (condensation) product thereof as component (B) and an ultraviolet absorber as component (C) are subjected to severe conditions. It was found that the adhesiveness to the substrate was maintained at a high level even after boiling in water.

By coating the resin composition of the present invention on a substrate to form a resin layer, it can be used for optical filters useful for applications such as optical devices, display devices, mechanical parts, electric/electronic parts, and the like. .

Claims (6)

(A) a thermoplastic resin,
(B) at least one selected from the group consisting of an epoxy group-containing silane coupling agent, a hydrolyzate thereof, and a hydrolytic condensate thereof; and (C) an ultraviolet absorber having a thioether bond. resin composition. 2. The resin composition according to claim 1, wherein the UV absorber of component (C) is a compound represented by the following formula (1).

[In formula (1),
R ¹ represents a cyano group, an acyl group, a carboxylic acid ester group or an amide group,
^R2 represents a hydrogen atom, a cyano group, an acyl group, a carboxylic acid ester group, an amide group, a hydrocarbon group or a heteroaryl group;
When both R ¹ and R ² are an acyl group, a carboxylic acid ester group or an amide group, R ¹ and R ² may be linked together to form a ring,
R3 represents a hydrogen atom or an alkyl group ^,
R ⁴ represents a hydrogen atom, an organic group or a polar functional group, multiple R ⁴ may be the same or different,
^R5 represents an organic group,
X represents a sulfur atom . ] 3. The resin composition according to claim 1, wherein the component (B) contains a hydrolyzate and/or a hydrolyzed condensate of an epoxy group-containing silane coupling agent. 4. The resin composition according to any one of claims 1 to 3, further comprising (D) a near-infrared absorbing dye and/or a visible light absorbing dye. An optical filter comprising a substrate and a resin layer formed on the substrate and obtained by curing the resin composition according to any one of claims 1 to 4. A sensor comprising an optical filter according to claim 5 .