JP6052891B2 - Thermosetting resin composition and its near infrared cut filter - Google Patents

Description

  The present invention relates to a thermosetting resin composition containing a near-infrared absorbing dye and a near-infrared cut filter (optical filter) using the same.

Imaging devices such as CCD (Charge Coupled Device) and CMOS (Complementary Metal Oxide Semiconductor) used in digital cameras have spectral sensitivity in the near infrared region near the visible region to 1100 nm. The human eye can feel light having a wavelength in the vicinity of 400 nm to 700 nm. Therefore, since there is a large difference in spectral sensitivity between the image sensor and the human eye, it is necessary to provide a near-infrared cut filter that absorbs the near-infrared region in front of the image sensor to correct the visual sensitivity of the human eye. It is known.

  As a near-infrared cut filter used for an image sensor, a glass filter in which CuO is added to phosphate glass is known as described in Patent Document 1. However, this glass having near infrared absorption ability is very expensive. Moreover, since it is glass, there exists a problem in workability, the freedom degree of the design of an optical characteristic is narrow, and the response | compatibility to a spherical surface is also complicated. Furthermore, there is a limit to reducing the thickness of the glass, and there are problems in securing space and reducing the weight when incorporated into an imaging optical system. Therefore, in order to produce a new near-infrared cut filter that can be formed into a thin film or a spherical surface, it has been desired to develop a resin incorporating near-infrared absorption ability.

Then, development which produces a near-infrared cut filter by coating the resin composition containing a near-infrared absorption pigment | dye on the surface of an image pick-up element or a filter base material is performed. However, since the filter produced by this method has insufficient heat resistance, development of a filter with higher heat resistance has been strongly desired.

In order to solve these problems, as described in Patent Document 2, a method of adding an antioxidant has also been proposed, but it is still not sufficient and is preferable from the viewpoint of productivity. Therefore, another method for improving heat resistance is necessary.

  Against this background, in recent years, there has been a strong demand for the development of a near-infrared cut filter having high workability and heat resistance and a resin composition for producing the same.

JP 62-128943 A Japanese Patent No. 4232062 WO2012 / 137837

  An object of this invention is to provide the near-infrared cut filter excellent in workability and heat resistance produced using a resin composition, especially a thermosetting resin composition, and it.

  As a result of intensive studies, the present inventors have solved the above-mentioned problems with a resin composition comprising a thermosetting resin and a near-infrared absorbing dye described in Patent Document 3 and a near-infrared cut filter. As a result, the present invention was completed.

（式中、Ｒ_１がそれぞれ独立に炭素数１〜５の置換基を有してもよいアルキル基又は炭素数１〜５の置換基を有してもよいアルコキシアルキル基を示し、Ｒ_２はハロゲン原子、炭素数１〜５の置換基を有してもよいアルキル基、炭素数１〜５の置換基を有してもよいアルコキシ基又はニトロ基、ｐは０又は１の整数を示し、Ｙは水素原子又は塩素原子、Ｘがトリス（トリフルオロメタンスルホニル）メチドアニオンである。）
（Ｂ）エポキシ樹脂
メタクリル酸グリシジル骨格のみで構成された重合体、あるいはメタクリル酸グリシジル骨格を主としてアクリル酸、アクリル酸エステル、メタクリル酸、メタクリル酸エステル、ビニル置換芳香族化合物のいずれかの組み合わせで構成されるランダム共重合体であるエポキシ樹脂、
（Ｃ）エポキシ樹脂硬化剤
２個以上のカルボキシル基を有し、脂肪族炭化水素基を主骨格とする多価カルボン酸であるエポキシ樹脂硬化剤、
（２）近赤外線吸収色素（Ａ）の中で、上記式（２）で示されるシアニン化合物と、上記式（１）で示されるシアニン化合物の含有量の比が１：０．３〜１：０．５であることを特徴とする（１）に記載の熱硬化性樹脂組成物、
（３）エポキシ樹脂硬化剤（Ｃ）が、炭素数２乃至４の脂肪族炭化水素基を主骨格とする２価カルボン酸である（１）または（２）に記載の熱硬化性樹脂組成物、
（４）エポキシ樹脂（Ｂ）のエポキシ当量が２８０〜３５０ｇ／ｅｑ.である（１）乃至（３）のいずれか一つに記載の熱硬化性樹脂組成物、
（５）エポキシ樹脂（Ｂ）の重量平均分子量が５０００〜２００００である（１）乃至（４）のいずれか一つに記載の熱硬化性樹脂組成物、
（６）近赤外線吸収色素（Ａ）が下記式（３）及び式（４）であることを特徴とする（１）乃至（５）のいずれか一つに記載の熱硬化性樹脂組成物、

（式中、Ｒ_３がそれぞれ独立にメチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル基、ｔ−ブチル基、メトキシエチル基、ｎ−ブトキシエチル基、Ｙは水素原子又は塩素原子、Ｘがトリス（トリフルオロメタンスルホニル）メチドアニオンである。）
（７）（１）乃至（６）のいずれか一つに記載の熱硬化性樹脂組成物から得られる硬化物、
（８）（１）乃至（７）のいずれか一つに記載の熱硬化性樹脂組成物を用いて成形し得られた近赤外線カットフィルタ、
（９）（８）に記載の近赤外線カットフィルタを具備した撮像素子、
に関する。 That is, the present invention
(1)
A thermosetting resin composition comprising the following (A) to (C):
(A) Near-infrared absorbing dye comprising two types of cyanine compounds of the following formulas (1) and (2),

(In the formula, each R ₁ independently represents an alkyl group which may have a substituent having 1 to 5 carbon atoms or an alkoxyalkyl group which may have a substituent having 1 to 5 carbon atoms, and R ₂ represents A halogen atom, an alkyl group which may have a substituent having 1 to 5 carbon atoms, an alkoxy group or a nitro group which may have a substituent having 1 to 5 carbon atoms, p represents an integer of 0 or 1, Y is a hydrogen atom or a chlorine atom, and X is a tris (trifluoromethanesulfonyl) methide anion.)
(B) Epoxy resin A polymer composed only of a glycidyl methacrylate skeleton, or a glycidyl methacrylate skeleton mainly composed of any combination of acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, and vinyl-substituted aromatic compound. An epoxy resin, which is a random copolymer
(C) Epoxy resin curing agent An epoxy resin curing agent which is a polyvalent carboxylic acid having two or more carboxyl groups and having an aliphatic hydrocarbon group as a main skeleton,
(2) In the near-infrared absorbing dye (A), the ratio of the content of the cyanine compound represented by the above formula (2) and the cyanine compound represented by the above formula (1) is 1: 0.3 to 1: The thermosetting resin composition according to (1), which is 0.5,
(3) The thermosetting resin composition according to (1) or (2), wherein the epoxy resin curing agent (C) is a divalent carboxylic acid having an aliphatic hydrocarbon group having 2 to 4 carbon atoms as a main skeleton. ,
(4) The thermosetting resin composition according to any one of (1) to (3), wherein the epoxy equivalent of the epoxy resin (B) is 280 to 350 g / eq.
(5) The thermosetting resin composition according to any one of (1) to (4), wherein the epoxy resin (B) has a weight average molecular weight of 5000 to 20000.
(6) The thermosetting resin composition according to any one of (1) to (5), wherein the near-infrared absorbing dye (A) is represented by the following formula (3) and formula (4):

(In the formula, each R ₃ independently represents a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, a methoxyethyl group, or an n-butoxyethyl group. Y represents a hydrogen atom or a chlorine atom, and X represents a tris (trifluoromethanesulfonyl) methide anion.)
(7) A cured product obtained from the thermosetting resin composition according to any one of (1) to (6),
(8) A near infrared cut filter obtained by molding using the thermosetting resin composition according to any one of (1) to (7),
(9) An image sensor provided with the near infrared cut filter according to (8),
About.

  By this invention, the resin composition which can produce the near-infrared cut filter with high heat resistance was able to be provided.

The curable resin composition of the present invention contains a near-infrared absorbing dye (A), an epoxy resin (B), and an epoxy resin curing agent (C).

  The counter anion of the near-infrared absorbing dye (A) is not particularly limited, but from the viewpoint of heat resistance and transparency of the cured product (optical filter), bis (perhalogenoalkylsulfonyl) imide represented by the following formula (5) An anion or a tris (perhalogenoalkylsulfonyl) methide anion represented by the following formula (6) is preferable. More preferred is a tris (perhalogenoalkylsulfonyl) methide anion, and still more preferred is a tris (trifluoromethylsulfonyl) methide anion in which n is 1 and A is a fluorine atom in the following formula (6).

（式中、ｘは１〜５、Ａはフッ素原子、塩素原子、臭素原子又はヨウ素原子を示す。）

(In the formula, x represents 1 to 5, and A represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.)

（式中、ｘは１〜５、Ａはフッ素原子、塩素原子、臭素原子又はヨウ素原子を示す。）

(In the formula, x represents 1 to 5, and A represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.)

Although the specific example of the near-infrared absorption pigment | dye (A) contained in the near-infrared cut off filter of this invention is given to the following, it is not limited to these, What is necessary is just a compound which absorbs near-infrared rays. In the case of a cyanine compound, compounds 16 to 45 in Japanese Patent No. 4635007, formulas (3) to (32) in Japanese Patent No. 3786408, compounds 1 to 16 in Japanese Patent Application Laid-Open No. 2007-153836, and Japanese Patent Application Laid-Open No. 2008-88426 are disclosed. Compounds 16 to 57 in In the case of a polymethine compound, the compound No. in JP-A-58-219090 is disclosed. (1)-(20) is mentioned. In the case of a diimonium compound, No. 4 in Table 1 of Japanese Patent No. 4800769. 1-150, No. 1 in Table 1 of WO2006 / 120888. 1 to 20, No. 1 in Tables 1 to 3 of JP-A-2003-96040. 1 to 36, No. 1 in Table 1 of JP2007-197492A. 1-21 is mentioned. In the case of a phthalocyanine compound, compounds described in the first group and the second group in JP-A-2000-26748 can be mentioned. In the case of a naphthalocyanine compound, the compounds described in Table 1 of JP-A No. 11-152415 can be mentioned. Or the metal dithiol complex of following formula (7), the metal diamine complex of following formula (8), etc. are mentioned.

（式中、Ｒ_１０ 〜Ｒ_１３ は互いに同一もしくは相異なる水素原子、ハロゲン原子、シアノ基、アシル基、カルバモイル基、アルキルアミノカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、置換又は無置換のアルキル基、あるいは置換又は無置換のアリール基を表し、かつ、隣り合う２個の置換基が連結基を介して繋がっていてもよい。また、Ｍはニッケル、白金、パラジウム、又は銅の金属である。）

(Wherein R _{10 to} R ₁₃ are the same or different from each other, hydrogen atom, halogen atom, cyano group, acyl group, carbamoyl group, alkylaminocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, substituted or unsubstituted alkyl. Represents a group, or a substituted or unsubstituted aryl group, and two adjacent substituents may be connected via a linking group, and M is a metal of nickel, platinum, palladium, or copper. .)

（式中、Ｒ_１４ 〜Ｒ_１７ は互いに同一もしくは相異なる水素原子、ハロゲン原子、シアノ基、アシル基、カルバモイル基、アルキルアミノカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、置換又は無置換のアルキル基、あるいは置換又は無置換のアリール基を表し、かつ、隣り合う２個の置換基が連結基を介して繋がっていてもよい。また、Ｍはニッケル、白金、パラジウム、又は銅の金属である。）

(Wherein R _{14 to} R ₁₇ are the same or different from each other, hydrogen atom, halogen atom, cyano group, acyl group, carbamoyl group, alkylaminocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, substituted or unsubstituted alkyl group) Represents a group, or a substituted or unsubstituted aryl group, and two adjacent substituents may be connected via a linking group, and M is a metal of nickel, platinum, palladium, or copper. .)

These substituents are not particularly limited, but are preferably unsubstituted (hydrogen atoms) for easy control of the maximum absorption wavelength.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A fluorine atom, a chlorine atom and an iodine atom are preferable, and a chlorine atom is particularly preferable.

Examples of the acyl group include, but are not limited to, acetyl group, ethylcarbonyl group, propylcarbonyl group, butylcarbonyl group, pentylcarbonyl group, hexylcarbonyl group, benzoyl group, pt-butylbenzoyl group, and the like. .

Examples of the alkylaminocarbonyl group include, but are not limited to, methylaminocarbonyl group, ethylaminocarbonyl group, n-propylaminocarbonyl group, n-butylaminocarbonyl group, sec-butylaminocarbonyl group, n-pentylamino. Carbonyl group, n-hexylaminocarbonyl group, n-heptylaminocarbonyl group, n-octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dimethylaminocarbonyl group, diethylaminocarbonyl group, di-n-propylaminocarbonyl group, di -N-butylaminocarbonyl group, di-sec-butylaminocarbonyl group, di-n-pentylaminocarbonyl group, di-n-hexylaminocarbonyl group, di-n-heptylaminocarbonyl group, di-octylaminocarbonyl Group and the like.

Examples of alkoxycarbonyl groups include, but are not limited to, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, iso-propoxycarbonyl group, n-butoxycarbonyl group, iso-butoxycarbonyl group, sec-butoxycarbonyl Group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, iso-pentyloxycarbonyl group, neo-pentyloxycarbonyl group, 1,2-dimethyl-propyloxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl Group, 1,3-dimethyl-butyloxycarbonyl group, 1-iso-propylpropyloxycarbonyl group, 1,2-dimethylbutyloxycarbonyl group, n-heptyloxycarbonyl group, 1,4-dimethyl Pentyloxycarbonyl group, 2-methyl-1-iso-propylpropyloxycarbonyl group, 1-ethyl-3-methylbutyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, 3-methyl-iso Straight chain having 2 to 20 carbon atoms such as -propylbutyloxycarbonyl group, 2-methyl-1-iso-propyloxycarbonyl group, 1-t-butyl-2-methylpropyloxycarbonyl group, n-nonyloxycarbonyl group Or a branched alkyloxycarbonyl group etc. are mentioned.

Examples of the aryloxycarbonyl group include, but are not limited to, a phenyloxycarbonyl group, a naphthyloxycarbonyl group, a trioxycarbonyl group, a xylyloxycarbonyl group, a chlorophenyloxycarbonyl group, and the like.

Among the substituted or unsubstituted alkyl groups, specific examples of the unsubstituted alkyl group include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl. Group, t-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, cyclopentyl group, 1,2-dimethylpropyl group, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1 -Iso-propylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2-methyl-1-iso-propylpropyl group, 1-ethyl-3-methylbutyl group, n -Octyl group, 2-ethylhexyl group, 3-methyl 1-iso-propylbutyl group, 2-methyl-1-iso-propyl group, 1-t-butyl-2-methyl Rupuropiru group, n- nonyl, 3,5,5 linear 1 to 20 carbon atoms such as trimethyl hexyl group, and a hydrocarbon group branched or cyclic. Among these, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and a t-butyl group are preferable, and a methyl group and an ethyl group are particularly preferable.

The substituted alkyl group is a group in which at least one hydrogen of the above-mentioned unsubstituted alkyl group is substituted with various functional groups. For example, an alkoxyalkyl group in which an hydrogen of an unsubstituted alkyl group is substituted with an alkoxy group, an alkoxyalkoxyalkyl group in which a hydrogen of an unsubstituted alkyl group is substituted with an alkoxyalkoxy group, or a hydrogen in an unsubstituted alkyl group is alkoxyalkoxy Alkoxyalkoxyalkoxyalkyl groups substituted by alkoxy groups, halogenated alkyl groups in which hydrogen of unsubstituted alkyl groups is substituted by halongen, aminoalkyl groups in which hydrogen of unsubstituted alkyl groups is substituted by amino groups, unsubstituted An alkylaminoalkyl group in which the hydrogen of the alkyl group is substituted with an alkylamino group, a dialkylaminoalkyl group, an alkoxycarbonylalkyl group, an alkylaminocarbonylalkyl group, an alkoxysulfonylalkyl group, and the like.

Specific examples of the alkoxyalkyl group include methoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, n-butoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, methoxyethoxymethyl group, ethoxyethoxy. Examples thereof include an ethyl group, a dimethoxymethyl group, a diethoxymethyl group, a dimethoxyethyl group, and a diethoxyethyl group. Examples of the halogenated alkyl group include a chloromethyl group, a 2,2,2-trichloroethyl group, and trifluoromethyl. Group, 1,1,1,3,3,3-hexafluoro-2-propyl group and the like. Of these, a methoxyethyl group, an ethoxyethyl group, a propoxyethyl group, and an n-butoxyethyl group are preferable, and a methoxyethyl group is particularly preferable.

Among the substituted or unsubstituted aryl groups, examples of the unsubstituted group include a phenyl group, a naphthyl group, and a biphenyl group. The substituted aryl group is a group in which at least one hydrogen of the above unsubstituted aryl group is substituted with various functional groups. For example, the substituted phenyl group includes a chlorophenyl group, a dichlorophenyl group, a trichlorophenyl group, a bromophenyl group. Group, fluorophenyl group, pentafluorophenyl group, halogenated phenyl group such as phenyl iodide group; tolyl group, xylyl group, mesityl group, ethylphenyl group, dimethylethylphenyl group, iso-propylphenyl group, t-butylphenyl group Group, alkyl derivative substituted phenyl group such as t-butylmethylphenyl group, octylphenyl group, nonylphenyl group, trifluoromethylphenyl group; methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group, isopropoxyphenyl group, hexyloxyphenyl Group Rohexyloxyphenyl group, octyloxyphenyl group, 2-ethylhexyloxyphenyl group, 3,5,5-trimethylhexyloxyphenyl group, methylethoxyphenyl group, dimethoxyphenyl group, 1-methoxy-5-ethoxyphenyl group, 1 -Methoxy-2-ethoxyphenyl group, 1-methoxy-3-ethoxyphenyl group, 1-methoxy-4-ethoxyphenyl group, 1-ethoxy-2-methoxyphenyl group, 2-methoxy-3-ethoxyphenyl group, 2 -Methoxy-4-ethoxyphenyl group, 2-methoxy-5-ethoxyphenyl group, 1-ethoxy-4-methoxyphenyl group, 2-methoxy-3-ethoxyphenyl group, diethoxyphenyl group, ethoxyethoxyphenyl group, di (Ethoxyethoxy) phenyl group, ethoxyethoxy Ethoxyphenyl group, di (ethoxyethoxyethoxy) phenyl group, 3-methoxy-4- (2-methoxyethoxy) phenyl group, 3-methoxy-4- (2-ethoxyethoxy) siphenyl group, 3-ethoxy-4 (2- Methoxyethoxy) siphenyl group, 3-ethoxy-4- (2-ethoxyethoxy) siphenyl group, 3-propoxy-4- (2-methoxyethoxy) phenyl group, 3-propoxy-4- (2-ethoxyethoxy) siphenyl group, 3 -Iso-propoxy-4- (2-methoxyethoxy) cyphenyl group, 3-iso-propoxy-4- (2-ethoxyethoxy) siphenyl group, 2- (2-hydroxy) -3-methoxyphenyl group, 3-methoxy- 4- (2-hydroxyethoxy) phenyl group, chloromethoxyphenyl group, chloroethoxypheny Alkoxy-substituted phenyl groups such as thiol groups; alkylthio-substituted phenyl groups such as methylthiophenyl group, ethylthiophenyl group, t-butylthiophenyl group, di-tert-butylthiophenyl group, 2-methyl-1-methylthiophenyl group N, N-dimethylaminophenyl group, N, N-diethylaminophenyl group, N, N-dipropylaminophenyl group, N, N-dibutylaminophenyl group, N, N-diamylaminophenyl group, N, N -Dihexylaminophenyl group, N-methyl-N-ethylaminophenyl group, N-butyl-N-ethylaminophenyl group, N-hexyl-N-ethylaminophenyl group, 4- (N, N-dimethylamino)- Ethylphenyl group, 4- (N, N-diethylamino) -ethylphenyl group, 3- (N, N-dimethylamino) ) - ethylphenyl group, 2-(N, N-dimethylamino) - ethyl alkylamino phenyl group such as a phenyl group, and the like.

Examples of the substituted naphthyl group include halogenated naphthyl groups such as chloronaphthyl group, dichloronaphthyl group, trichloronaphthyl group, bromonaphthyl group, fluoronaphthyl group, pentafluoronaphthyl group and iodide naphthyl group; ethylnaphthyl group, dimethylethyl Alkyl derivative substituted naphthyl groups such as naphthyl group, iso-propyl naphthyl group, t-butyl naphthyl group, t-butylmethyl naphthyl group, octyl naphthyl group, nonyl naphthyl group, trifluoromethyl naphthyl group; methoxy naphthyl group, ethoxy naphthyl group , Propoxynaphthyl group, hexyloxynaphthyl group, cyclohexyloxynaphthyl group, octyloxynaphthyl group, 2-ethylhexyloxynaphthyl group, 3,5,5-trimethylhexyloxynaphthyl group, methylethoxynaphthyl group Alkoxy group-substituted naphthyl groups such as dimethoxynaphthyl group, chloromethoxynaphthyl group, ethoxyethoxynaphthyl group, ethoxyethoxyethoxynaphthyl group; methylthionaphthyl group, ethylthionaphthyl group, t-butylthionaphthyl group, methylethylthionaphthyl group, butyl Alkylthio group-substituted naphth N, N-dimethylaminonaphthyl group such as methylthionaphthyl group; N, N-diethylaminonaphthyl group, N, N-dipropylaminonaphthyl group, N, N-dibutylaminonaphthyl group, N, N-dia Milaminonaphthyl group, N, N-dihexylaminonaphthyl group, N-methyl-N-ethylaminonaphthyl group, N-butyl-N-ethylaminonaphthyl group, N-hexyl-N-ethylaminonaphthyl group, 4- ( N, N-dimethylamino) -ethylnaphth Alkyl group such as 4- (N, N-diethylamino) -ethylnaphthyl group, 3- (N, N-dimethylamino) -ethylnaphthyl group, 2- (N, N-dimethylamino) -ethylnaphthyl group A naphthyl group is mentioned.

In addition to these, substituted or unsubstituted aryl groups include substituted or unsubstituted p-nitrophenyl groups, substituted or unsubstituted pyridyl groups, substituted or unsubstituted pyrrolidyl groups, substituted or unsubstituted piperidyl groups, substituted Alternatively, an unsubstituted morpholine group, a substituted or unsubstituted tetrahydropyridyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted furyl group, and the like are also included.

R ₁₀ of the metal complex compound represented by the above formulas (7) and (8)
Particularly preferred among the substituents represented by ˜R ₁₇ are the same or different alkyl group, phenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, ethylphenyl group, dimethylphenyl group, iso-propylphenyl. Group, t-butylphenyl group, t-butylmethylphenyl group, methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group, N, N-dimethylaminophenyl group, N, N-diethylaminophenyl group, N, N-dibutylamino Phenyl group, ethylnaphthyl group, dimethylethylnaphthyl group, iso-propylnaphthyl group, t-butylnaphthyl group, t-butylmethylnaphthyl group, methoxynaphthyl group, ethoxynaphthyl group, propoxynaphthyl group, methylthionaphthyl group, ethylthionaphthyl group Group, t-butylthiona Phthyl group, methylethylthionaphthyl group, butylmethylthionaphthyl group, N, N-dimethylaminonaphthyl group, N, N-diethylaminonaphthyl group, N, N-dipropylaminonaphthyl group, N, N-dibutylaminonaphthyl group, etc. A substituted or unsubstituted alkyl group having 3 to 20 carbon atoms, a phenyl group or a naphthyl group, and particularly preferred M is nickel.

  Examples of the near-infrared absorbing dyes of inorganic metals that can be used in combination include copper compounds such as metallic copper or copper sulfide, copper oxide, mixtures containing zinc oxide as a main component, tungsten compounds, mixtures containing titanium oxide as a main component, etc. However, it is not limited to these, and any compound that absorbs near-infrared light may be used. When these do not dissolve in the resin composition of the present invention, they can be mixed and dispersed by the following method.

  When the near-infrared absorbing dye contained in the near-infrared cut filter of the present invention does not dissolve in the resin composition of the present invention, it can be used by mixing and dispersing with other components while making the insoluble dye fine particles.

Examples of the mixing and dispersing method include a known method using a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, and the like, among which a sand mill (bead mill) is preferable. In the pulverization of the pigment particles in the sand mill (bead mill), it is preferable to use beads having a small particle diameter, and to perform the treatment under conditions that increase the pulverization efficiency by increasing the filling rate of the beads. Furthermore, it is preferable to remove beads and coarse particles used for dispersion by filtration, centrifugation, or the like after the pulverization treatment.

  The content of the near-infrared absorbing dye (A) used in the resin composition of the present invention is appropriately determined according to the target near-infrared cut rate.

Examples of the epoxy resin (B) include an epoxy resin that is a glycidyl etherified product of a phenol compound, an epoxy resin that is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, Glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, condensates of silicon compounds having an epoxy group with other silicon compounds, polymerizable unsaturated compounds having an epoxy group Examples thereof include copolymers with other polymerizable unsaturated compounds.

  Examples of the epoxy resin that is a glycidyl etherified product of the phenol compound include 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2, 3-hydroxy) phenyl] ethyl] phenyl] propane, bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, tetramethyl bisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S Dimethylbisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4′-biphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) ) Ethyl) phenyl] propane, 2,2'-methylene -Bis (4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phloroglucinol, di Examples thereof include phenols having an isopropylidene skeleton; phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene; and epoxy resins which are glycidyl etherified products of polyphenol compounds such as phenolized polybutadiene.

  Examples of the epoxy resin that is a glycidyl etherified product of the above-mentioned various novolak resins include, for example, phenols, cresols, ethylphenols, butylphenols, octylphenols, bisphenols such as bisphenol A, bisphenol F and bisphenol S, and naphthols. Examples include novolak resins made from phenol, phenol novolak resins containing xylylene skeletons, phenol novolac resins containing dicyclopentadiene skeletons, phenol novolac resins containing biphenyl skeletons, phenol novolac resins containing fluorene skeletons, and the like. .

Examples of the alicyclic epoxy resin include fats having an aliphatic ring skeleton such as 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate. Examples thereof include cyclic epoxy resins.
Examples of the aliphatic epoxy resin include glycidyl ethers of polyhydric alcohols such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, and pentaerythritol.
Examples of the heterocyclic epoxy resin include heterocyclic epoxy resins having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring.
Examples of the glycidyl ester epoxy resin include epoxy resins made of carboxylic acid esters such as hexahydrophthalic acid diglycidyl ester.
Examples of the glycidylamine-based epoxy resin include epoxy resins obtained by glycidylating amines such as aniline and toluidine.
Examples of epoxy resins obtained by glycidylation of the halogenated phenols include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated bisphenol S, and chlorinated bisphenol A. And epoxy resins obtained by glycidylation of halogenated phenols such as

  As a copolymer of a polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compounds, Marproof G-0115S, G-0130S, and G-0250S are commercially available products. G-1010S, G-1005S, G-0150M, G-2050M (manufactured by NOF Corporation), and the like. Examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, Examples thereof include glycidyl methacrylate and 4-vinyl-1-cyclohexene-1,2-epoxide. Examples of other polymerizable unsaturated compound copolymers include methyl (meth) acrylate, ether (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, and vinylcyclohexane. In particular, methyl (meth) acrylate, ether (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable.

  The weight average molecular weight of the epoxy resin is preferably 5000 to 250,000, more preferably 5000 to 20000, and still more preferably 5000 to 10,000.

  Moreover, the preferable epoxy equivalent of the said epoxy resin is 310-3300 g / eq., More preferably, it is 310-1700 g / eq., More preferably, it is 310-1000 g / eq.

You may use the said epoxy resin 1 type or in mixture of 2 or more types.

Examples of the epoxy resin curing agent (C) include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and polycarboxylic acids. In the present invention, the epoxy resin curing agent is preferably a polyvalent carboxylic acid from the viewpoint of heat resistance and transparency of the cured product, and most preferably a compound having two or more carboxylic anhydride groups in the molecule.

  Specific examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride Acid, methylhexahydrophthalic anhydride, glutaric anhydride, 2,4-diethyl glutaric anhydride, 3,3-dimethyl glutaric anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2, Acid anhydrides such as 3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride Is mentioned. In particular, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 2,4-diethylglutaric anhydride, butanetetracarboxylic anhydride, bicyclo [2,2, 1] Heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride Etc. are preferable from the viewpoint of light resistance, transparency, and workability.

  The polyvalent carboxylic acid is a compound having at least two carboxyl groups. In addition, when a geometric isomer or an optical isomer exists in the following compound, it is not particularly limited. As the polyvalent carboxylic acid, a bifunctional to hexafunctional carboxylic acid is preferable, for example, 1,2,3,4-butanetetracarboxylic acid, 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid. Alkyltricarboxylic acids such as acid and citric acid; aliphatic cyclic polyvalents such as phthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, cyclohexanetricarboxylic acid, nadic acid, and methylnadic acid Carboxylic acids; Multimers of unsaturated fatty acids such as linolenic acid and oleic acid, and dimer acids that are reduced products thereof; linear alkyl diacids such as malic acid are preferred; hexanedioic acid, pentanedioic acid, heptane Diacid, octanedioic acid, nonanedioic acid, and decanedioic acid are preferred. More preferable from the viewpoint of transparency of the product.

  In the curable resin composition of the present invention, the polyvalent carboxylic acid is preferably used in an amount of 0.01 to 20% by weight, more preferably 0.01 to 10% by weight, based on the epoxy resin. The use of 1 to 6.0% by weight is particularly preferred.

When a curing agent other than the aforementioned acid anhydride and / or polyvalent carboxylic acid is used as the epoxy resin curing agent, the proportion of the total amount of the acid anhydride and / or polyvalent carboxylic acid in the total curing agent is 30. % By weight or more is preferable, and 40% by weight or more is particularly preferable. Examples of the curing agent that can be used in combination include amine compounds, amide compounds, phenol compounds, and the like. Specific examples of curing agents that can be used include amines (1,4-butanediamine) and polyamide compounds (diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, linolenic acid dimer and ethylenediamine. Polyamide resins synthesized), polyhydric phenols (bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5 , 5′-tetramethyl- [1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis ( 4-hi Droxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1,4 Polycondensates with '-bis (chloromethyl) benzene, 1,4'-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, And the like, but are not limited to these, such as imidazole, trifluoroborane-amine complexes, guanidine derivatives, etc. These may be used alone or in combination The above may be used.

  The curable resin composition of the present invention can supplement the hardness of the cured product by using a coupling agent as necessary. Examples of coupling agents that can be used include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyl. Trimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltri Methoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloro Silane coupling agents such as propyltrimethoxysilane; isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate, Titanium coupling agents such as neoalkoxytri (pN- (β-aminoethyl) aminophenyl) titanate; Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytrisneodeca Noyl zirconate, neoalkoxytris (dodecanoyl) benzenesulfonyl zirconate, neoalkoxytris (ethylenediaminoethyl) zirconate, neoalco Examples include zirconium such as xylitol (m-aminophenyl) zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, and Al-propionate, or an aluminum coupling agent. These coupling agents may be used alone or in combination of two or more. A coupling agent adds 0.05-20 weight part normally with respect to the curable resin composition of this invention as needed, Preferably 0.1-10 weight part is added.

The curable resin composition of the present invention can be supplemented with mechanical strength and the like without impairing transparency by using a nano-order level inorganic filler as necessary. As a standard for the nano-order level, it is preferable from the viewpoint of transparency to use a filler having an average particle size of 500 nm or less, particularly an average particle size of 200 nm or less. Examples of inorganic fillers include powders such as crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, and talc. Alternatively, beads obtained by spheroidizing these may be used, but the present invention is not limited thereto. These fillers may be used alone or in combination of two or more. These inorganic fillers are used at a blending rate of 0 to 95% by weight in the curable resin composition of the present invention.

For the purpose of preventing coloration, the curable resin composition of the present invention may contain an amine compound as a light stabilizer, or a phosphorus compound and a phenol compound as an antioxidant.
Examples of the amine compound include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-6- Totramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3 , 9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mixed ester, decanedioic acid bis (2,2,6 , 6-Tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2,6,6, -tetrame Ru-4-piperidyl methacrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy -2,2,6,6-tetramethylpiperidine, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] bu Lumalonate, decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, N, N ′, N ", N"'-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl)- 4,7-diazadecane-1,10-diamine, dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexa Polycondensate of methylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3 , 5-Triazine- , 4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], dimethyl succinate And 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2,2,4,4-tetramethyl-20- (β-lauryloxycarbonyl) ethyl-7-oxa- 3,20-diazadispiro [5 · 1 · 11 · 2] heneicosan-21-one, β-alanine, N,-(2,2,6,6-tetramethyl-4-piperidinyl) -dodecyl ester / tetradecyl ester N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa 3,20-diazadispiro [5,1,11,2] heneicosane-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo- [5,1,11,2] -Heneicosane-20-propanoic acid dodecyl ester / tetradecyl ester, propanedioic acid, [(4-methoxyphenyl) -methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 2,2,6,6-tetramethyl-4-piperidinol higher fatty acid ester, 1,3-benzenedicarboxamide, N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl) Hindered amines such as octabenzone, benzophenone compounds such as octabenzone, 2- (2H-benzotriazol-2-yl) -4- (1,1,3, -Tetramethylbutyl) phenol, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimido-methyl) -5-methylphenyl Benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) benzotriazole, Reaction product of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol, 2- (2H-benzotriazol-2-yl)- Benzotriazole compounds such as 6-dodecyl-4-methylphenol, 2,4 Benzoate series such as di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5 Examples include triazine compounds such as [(hexyl) oxy] phenol, and hindered amine compounds are particularly preferable.

  Although it does not specifically limit as an amine compound which is said light stabilizer, The following commercial items can be used, for example, Ciba Specialty Chemicals products, such as TINUVIN765, TINUVIN770DF, TINUVIN144, TINUVIN123, TINUVIN622LD, TINUVIN152, CHIMASSORB944, etc. ADEKA products such as LA-52, LA-57, LA-62, LA-63P, LA-77Y, LA-81, LA-82, and LA-87.

  The phosphorus compound is not particularly limited, and examples thereof include 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-tert-butylphenyl) butane, distearyl pentaerythritol diphosphite, Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite , Dicyclohexylpentaerythritol diphosphite, tris (diethylphenyl) phosphite, tris (di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) ) Hos Ite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butyl) Phenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-ethylidenebis (4-methyl-6-tert-butyl) Phenyl) (2-tert-butyl-4-methylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4, '-Biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'- Biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenedi Phosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butyl) Ruphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl -Phenylphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl Examples include phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc.

  Although the said phosphorus compound is not specifically limited, A commercial item can also be used, for example, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB ADEKA products such as 260, ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 135A, ADK STAB 3010, and ADK STAB TPP.

  The phenol compound is not particularly limited, and examples thereof include 2,6-di-tert-butyl-4-methylphenol and n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2,4-di-tert-butyl-6-methylphenol, 1,6-hexanediol-bis -[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, pentaerythrine Lithyl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis- [2- [3- (3-tert-butyl-4-hydroxy-5- Methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol-bis [3- (3-t-butyl-5 -Methyl-4-hydroxyphenyl) propionate], 2,2'-butylidenebis (4,6-di-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2,2 '-Methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol) 2), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenol acrylate, 2- [1- (2-hydroxy-3,5-di-) tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6) -Tert-butylphenol), 2-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,4-di-tert-pentylphenol, 4,4'-thiobis (3-methyl-6) -Tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), bis [3,3-bis- (4′-hydroxy-3′-tert-butylphenyl) -butanoic acid] -glycol ester, 2,4-di-tert-butylphenol, 2,4-di-tert-pentyl Phenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, bis- [3,3-bis- (4 ′ -Hydroxy-3'-tert-butylphenyl) -butanoic acid] -glycol ester and the like.

Although the above-mentioned phenolic compound is not particularly limited, commercially available products can also be used. -20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90, ADK STAB AO-330, etc .; , Sumilizer MDP-S, Sumilizer BM-S, Sumilizer GM, Sumilizer GS (F), Sumilizer
Sumitomo Chemical products such as GP.

  In addition, a commercially available additive can be used as an anti-coloring agent for the resin. For example, Ciba Specialty Chemicals products such as THINUVIN 328, THINUVIN 234, THINUVIN 326, THINUVIN 120, THINUVIN 477, THINUVIN 479, CHIMASSORB 2020FDL, and CHIMASSORB 119FL may be mentioned.

  It is preferable to contain at least one of the above phosphorus compounds, amine compounds, or phenol compounds, and the amount of the compound is not particularly limited, but is based on the total weight of the curable resin composition of the present invention. And 0.005 to 5.0% by weight.

The near-infrared cut filter (optical filter) using the resin composition of the present invention may be provided on a base material or the base material itself. The substrate is not particularly limited as long as it can be generally used for an optical filter, but a substrate made of glass or resin is usually used. The thickness of the layer is usually about 0.05 μm to 10 mm, but is appropriately determined according to the purpose such as the near-infrared cut rate. Further, an image pickup device itself such as a CCD or CMOS can be used as a base material.

Examples of resin base materials used include vinyl compounds such as polyethylene, polycycloalkane, polycycloolefin, polystyrene, polyacrylic acid, polyacrylic ester, polyvinyl acetate, polyacrylonitrile, polyvinyl chloride, and polyvinyl fluoride. , And addition polymers of these vinyl compounds, polymethacrylic acid, polymethacrylic acid ester, polyvinylidene chloride, polyvinylidene fluoride, polyvinylidene polycyanide, vinylidene fluoride /
Copolymers of vinyl compounds or fluorine compounds such as trifluoroethylene copolymers, vinylidene fluoride / tetrafluoroethylene copolymers, vinylidene cyanide / vinyl acetate copolymers, polytrifluoroethylene, polytetrafluoroethylene, Fluorine-containing resins such as polyhexafluoropropylene, polyamides such as nylon 6 and nylon 66, polyimides, polyurethanes, polypeptides, polyesters such as polyethylene terephthalate, polyethers such as polycarbonate and polyoxymethylene, epoxy resins, polyvinyl alcohol, polyvinyl Examples include butyral.

  Although it does not specifically limit as a method of producing the infrared cut filter (optical filter) using the resin composition of this invention, For example, the following well-known method can be utilized. 1) A method of dissolving a near-infrared absorbing dye in a thermosetting resin and a curing agent to form a resin composition of the present invention, followed by molding and heat curing to produce a resin plate or film, 2) containing a near-infrared absorbing dye A method for coating a transparent resin plate, a transparent film, a transparent glass plate, or an image pickup device, and 3) a composition containing a near-infrared absorbing dye and a resin (adhesive). And a method of producing a laminated resin plate, a laminated resin film, or a laminated glass plate, and the like.

  In the method 1), a near-infrared absorbing dye is dissolved in a thermosetting resin and a curing agent and injected into a mold to form a resin composition of the present invention, which is cured by heat reaction or poured into a mold. And a method of molding by heating reaction until it becomes a hard product in the mold. Depending on the composition used, the processing temperature, filming (resin plate) conditions, etc. are somewhat different, but usually curing conditions at 100 to 200 ° C. for about 30 minutes to 5 hours are applied. The amount of the near-infrared absorbing dye added varies depending on the thickness of the resin plate or film to be produced, the absorption strength, the visible light transmittance, etc., but is usually about 0.01 to 30% by mass with respect to the mass of the base resin, preferably Is used in an amount of about 0.01 to 15% by mass.

  The method 2) is a method of dissolving a near-infrared absorbing dye in a binder resin to form a paint (resin composition of the present invention), and a solvent can also be used when forming a paint (resin composition of the present invention). . As the solvent, a halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvent, or a mixed solvent thereof can be used. The concentration of the near-infrared absorbing dye varies depending on the thickness of the coating to be produced, the absorption intensity, and the visible light transmittance, but is about 0.01 to 30% by mass relative to the binder resin. The coating material thus obtained is coated on a transparent resin plate, transparent film, transparent glass plate, or imaging device with a spin coater, bar coater, roll coater, gravure coater, offset coater, spray, etc. An absorption filter or an image sensor including the absorption filter can be obtained.

The near-infrared absorbing optical filter of the present invention is not limited to the imaging device application or the front plate of the display, but needs to cut near-infrared rays. For example, the near-infrared absorbing optical filter is also used for filter films such as heat insulating films, optical products, and sunglasses. I can do it.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples. Here, the part represents part by weight unless otherwise specified.

Example 1
In a glass separable flask equipped with a stirrer and a thermometer, 50.0 parts of glycidyl methacrylate skeleton random polymer (manufactured by NOF Corporation, Marproof G-0150M weight average molecular weight 10,000) as an epoxy resin (B), 100 parts of methyl ethyl ketone was added and dissolved by stirring at 20-35 ° C. for 2 hours. Next, as a near infrared absorbing dye (A), a compound represented by the following formula (9) (λmax in chloroform: 831 nm, see JP-A-2008-88426) 0.500 parts, and a compound represented by the following formula (10) (λmax in chloroform: 758 nm, see JP-A-2008-88426) 0.250. Part was added and stirred at 20-35 ° C. until uniform. Furthermore, 0.500 parts of butanedioic acid (1.00% by weight based on the epoxy resin (A)) as an epoxy resin curing agent (C) is added and stirred at 20 to 35 ° C. for 1 hour until uniform. A resin composition of the present invention was obtained. This resin composition is dropped onto a glass substrate placed on a spin coater, and the substrate surface is coated by rotating the substrate at 1000 rpm for 30 seconds, and then dried at 80 ° C. for 10 minutes to remove the solvent, and 150 Thermosetting at 3 ° C. for 3 hours gave an optical filter.
The obtained optical filter was measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-visible spectrophotometer UV-3150), and the absorbance of the optical filter was measured in the range of 300 to 1100 nm at a sampling pitch of 1 nm. Table 1 below shows the absorbance at the maximum absorption wavelength (793 nm) of the spectral waveform at each stage after drying the optical filter at 80 ° C. for 10 minutes, thermosetting at 150 ° C. for 3 hours, and standing at 210 ° C. for 10 minutes. Show.

Table 1

Comparative Example 1
As the near-infrared absorbing dye (A), an optical filter was prepared in the same manner as in Example 1 except that the dye to be added was changed to only 0.500 part of the compound of formula (9).

Comparison of heat resistance Evaluation of heat resistance was carried out by heat-curing each optical filter obtained in Example 1 and Comparative Example 1 in the same manner as in Example 1, and then heating at 210 ° C. for 10 minutes, and then each optical filter. Using the same spectrophotometer, the absorbance at the maximum absorption wavelength (793 nm) of the spectral waveform is measured, the residual ratio of the absorbance after thermosetting (150 ° C., 3 hours), and the heat resistance test (210 ° C., 10 minutes) The residual ratio of the absorbance was calculated from the following formula (I) and formula (II), and each was compared. The calculation results are shown in Table 2 below. By this comparison, it means that the higher the composition ratio, the better the heat resistance.

(I) (Residual rate after thermosetting (150 ° C., 3 hours)) =
(Absorbance after thermosetting (150 ° C., 3 hours)) / (Absorbance after drying at 80 ° C. for 10 minutes)

(II) (Remaining rate after heat test (210 ° C., 10 minutes)) =
(Absorbance after heat test (210 ° C., 10 minutes)) / (Absorbance after drying at 80 ° C. for 10 minutes)

Table 2

  From the results shown in Table 2, Example 1 showed a higher residual rate than Comparative Example 1 even after the heat resistance test. From the above, in the present invention, it can be said that the thermosetting resin composition containing the near-infrared absorbing dye composed of the above composition has excellent heat resistance in the production of the near-infrared cut filter.

About near-infrared cut performance comparison experiment The integral value of the half value width and the light absorbency to wavelength 600-1100nm was computed with the spectral waveform after 3-hour thermosetting of the optical filter of Example 1 and Comparative Example 1 at 150 degreeC. The larger the half-value width, the wider the band can be cut. The larger the integrated value of the absorbance, the more light can be cut. The larger the value, the higher the performance of the near-infrared cut filter. . The calculation results are shown in Table 3 below.

Table 3

  From the results in Table 3, Example 1 has a higher near-infrared cut performance than Comparative Example 1. From the above, in the present invention, it can be said that the thermosetting resin composition of the present invention composed of the above composition has excellent near-infrared cut performance as a near-infrared cut filter.

  Comparing heat resistance and near-infrared cut performance as described above, it can be said that the thermosetting resin composition composed of the composition of the present invention has excellent heat resistance as a near-infrared cut filter.

The thermosetting resin composition of the present invention and the near-infrared cut filter (optical filter) obtained thereby have little deterioration in near-infrared absorption performance even when a thermal load is applied, and has excellent weather resistance, and spin coating as a resin solution It is possible to easily form a film by such a method and has excellent workability, and is very useful as an optical filter for various applications, particularly as a near-infrared cut filter (optical filter) for an image sensor such as a CCD or CMOS. It is.

Claims (9)

A thermosetting resin composition comprising the following (A) to (C).
(A) Near-infrared absorbing dye comprises two kinds of cyanine compounds of the following formulas (1) and (2).

(In the formula, each R ₁ independently represents an alkyl group which may have a substituent having 1 to 5 carbon atoms or an alkoxyalkyl group which may have a substituent having 1 to 5 carbon atoms, and R ₂ represents A halogen atom, an alkyl group which may have a substituent having 1 to 5 carbon atoms, an alkoxy group or a nitro group which may have a substituent having 1 to 5 carbon atoms, p represents an integer of 0 or 1, Y is a hydrogen atom or a chlorine atom, and X is a tris (trifluoromethanesulfonyl) methide anion.)
(B) Epoxy resin A polymer composed only of a glycidyl methacrylate skeleton, or a glycidyl methacrylate skeleton mainly, in any combination of methyl (meth) acrylate, ether (meth) acrylate, benzyl (meth) acrylate, and styrene An epoxy resin which is a random copolymer composed.
(C) Epoxy resin curing agent An epoxy resin curing agent which is a polyvalent carboxylic acid having two or more carboxyl groups and having an aliphatic hydrocarbon group as a main skeleton. In the near-infrared absorbing dye (A), the content ratio of the cyanine compound represented by the above formula (2) and the cyanine compound represented by the above formula (1) is 1: 0.3 to 1: 0.5. The thermosetting resin composition according to claim 1, wherein The thermosetting resin composition according to claim 1 or 2, wherein the epoxy resin curing agent (C) is a divalent carboxylic acid having an aliphatic hydrocarbon group having 2 to 4 carbon atoms as a main skeleton. The thermosetting resin composition according to any one of claims 1 to 3, wherein an epoxy equivalent of the epoxy resin (B) is 280 to 350 g / eq. The thermosetting resin composition according to any one of claims 1 to 4, wherein the epoxy resin (B) has a weight average molecular weight of 5,000 to 20,000. The thermosetting resin composition according to any one of claims 1 to 5, wherein the near-infrared absorbing dye (A) is represented by the following formulas (3) and (4).

(In the formula, each R ₃ independently represents a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, a methoxyethyl group, or an n-butoxyethyl group. Y represents a hydrogen atom or a chlorine atom, and X represents a tris (trifluoromethanesulfonyl) methide anion.) Hardened | cured material obtained from the thermosetting resin composition as described in any one of Claims 1 thru | or 6. The near-infrared cut filter obtained by shape | molding using the thermosetting resin composition as described in any one of Claims 1 thru | or 7. An imaging device comprising the near-infrared cut filter according to claim 8.