JP2014214262A - Thermosetting resin composition and near-infrared cut filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that can be used to manufacture a near-infrared cut filter having high heat resistance and to provide a near-infrared cut filter having high heat resistance manufactured by using the resin composition, particularly, a near-infrared cut filter for an image pickup element such as CCD, CMOS or the like.SOLUTION: A curable resin composition comprises an epoxy resin, a curing agent for epoxy resin and a near-infrared ray absorbing dyestuff. An epoxy resin having a silicone skeleton produced by reacting, with water, a modified silicone oil produced by condensation of a silanol-terminated silicone oil and an epoxy group-containing silicon compound is used as the epoxy resin.

Description

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

  Image sensors such as CCDs and CMOSs used in digital cameras have a spectral sensitivity over the near infrared region from the visible region to near 1100 nm, whereas the human eye has a wavelength around 400 nm to 700 nm. Can feel the light. 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 obtained by adding CuO to a phosphate glass disclosed in Patent Document 1 is known. However, this glass having near infrared absorption ability is very expensive. Moreover, since it is glass, there exists a problem in workability, and the freedom degree of design of an optical characteristic is also narrow. Furthermore, therefore, the development of compositions and filters incorporating new near infrared absorption capabilities has been desired.

  Then, development which produces a near-infrared cut filter is performed by coating the image pick-up element surface or the filter base-material surface with the resin composition containing a near-infrared absorption pigment | dye. 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, a method of adding an antioxidant of Patent Document 2 has also been proposed, but it is still not sufficient and is not preferable from the viewpoint of productivity, and thus improves heat resistance. Other ways to make it necessary are 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-A 62-128943 Patent No. 432062 WO2012 / 137837

  An object of the present invention is to provide a thermosetting resin composition, and a near-infrared cut filter having high workability and heat resistance produced using the same.

  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は互いに同一であっても異なっていてもよく、炭素数１〜１０の直鎖状、分岐状もしくは環状のアルキル基、炭素数６〜１４のアリール基、あるいは炭素数２〜１０のアルケニル基を表し、ｍは平均値で２〜２０００を表す。）

（式中、Ｘはエポキシ基を有する置換基を、Ｒ_２は炭素数１〜１０の直鎖状、分岐状、環状のアルキル基又は炭素数６〜１０の芳香族炭化水素基を有するアリール基、Ｒ_３は、炭素数１〜１０の直鎖状、分岐状もしくは環状のアルキル基、ｐは０、１、２の整数、ｑは（３−ｐ）、を表す。）
（４）エポキシ樹脂硬化剤（Ｂ）が多価カルボン酸樹脂である（１）乃至（３）のいずれか一つに記載の硬化性樹脂組成物、
（５）多価カルボン酸樹脂が下記の（ｃ）及び（ｄ）を含む化合物の付加重合体である、（４）に記載の硬化性樹脂組成物、
（ｃ）；分子内に２つ以上の水酸基を有する多価アルコール化合物、
（ｄ）；分子内に１つ以上の酸無水物基を有する化合物、
（６）多価カルボン酸樹脂が下記の（ｃ）〜（ｅ）を含む化合物の付加重合体である（４）に記載の硬化性樹脂組成物、
（ｃ）；分子内に２つ以上の水酸基を有する多価アルコール化合物、
（ｄ）；分子内に１つ以上の酸無水物基を有する化合物、
（ｅ）；両末端カルビノール変性シリコーンオイル、
（７）下記の（ｌ）〜（ｎ）を特徴とする（６）に記載の硬化性樹脂組成物、
（ｌ）；分子内に２つ以上の水酸基を有する多価アルコール化合物（ｃ）が下記式（３）の構造を有する、
（ｍ）；分子内に１つ以上の酸無水物基を含有する化合物（ｄ）が下記式（４）乃至（１１）からなる群より選択される一種以上である、
（ｎ）；両末端カルビノール変性シリコーンオイル（ｅ）が下記式（１２）の構造を有する、

（式中、Ｒ_６、Ｒ_７はそれぞれ独立して炭素数１〜１０のアルキレン基を、ｍは平均値で１〜１０００を表す。）

（式中、Ｒ_４はそれぞれ独立して炭素数１〜１０のアルキレン基又は炭素数１〜１０のエーテル結合を含むアルキレン基、Ｒ_５はそれぞれ独立してメチル基又はフェニル基、ｎは平均値で１〜１０００、を表す。）
（８）近赤外線吸収色素（Ｃ）が、シアニン化合物、ポリメチン化合物、ジイモニウム化合物、フタロシアニン化合物、ナフタロシアニン化合物、金属ジチオール錯体、金属ジアミン錯体から選択される、少なくとも一種類を含有することを特徴とする（１）乃至（７）のいずれか一つに記載の樹脂組成物、
（９）近赤外線吸収色素（Ｃ）が、少なくとも１種類のシアニン化合物であることを特徴とする（１）乃至（７）のいずれか一つに記載の樹脂組成物、
（１０）（９）に記載のシアニン化合物のメチン鎖の炭素数が５以上であることを特徴とする（１）乃至（７）のいずれか一つに記載の樹脂組成物、
（１１）（１）乃至（１０）のいずれか一つに記載の樹脂組成物を用いた近赤外線カットフィルタ、
（１２）（１１）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 resin composition containing an epoxy resin (A) and an epoxy resin curing agent (B), a near-infrared absorbing dye (C),
(2) The resin composition according to (1), wherein the epoxy resin (A) is a silicone skeleton epoxy resin,
(3) The curable resin composition according to (1) or (2), wherein the silicone skeleton epoxy resin is synthesized through the following two-step reaction;
First stage reaction; condensation reaction of silanol-terminated silicone oil (a) represented by general formula (1) and epoxy group-containing silicon compound (b) represented by general formula (2);
Second stage reaction; dealcoholization hydrolysis condensation reaction of alkoxy group by reaction of the reactant obtained in the first stage reaction and added water;

(In the formula, R ₁ may be the same or different from each other, and is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or 2 carbon atoms. 10 represents an alkenyl group, and m represents an average value of 2 to 2000.)

(In the formula, X is a substituent having an epoxy group, R ₂ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aryl group having an aromatic hydrocarbon group having 6 to 10 carbon atoms. , R ₃ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, p represents an integer of 0, 1, 2 and q represents (3-p).)
(4) The curable resin composition according to any one of (1) to (3), wherein the epoxy resin curing agent (B) is a polyvalent carboxylic acid resin,
(5) The curable resin composition according to (4), wherein the polyvalent carboxylic acid resin is an addition polymer of a compound containing the following (c) and (d):
(C) a polyhydric alcohol compound having two or more hydroxyl groups in the molecule,
(D); a compound having one or more acid anhydride groups in the molecule;
(6) The curable resin composition according to (4), wherein the polyvalent carboxylic acid resin is an addition polymer of a compound containing the following (c) to (e):
(C) a polyhydric alcohol compound having two or more hydroxyl groups in the molecule,
(D); a compound having one or more acid anhydride groups in the molecule;
(E); carbinol-modified silicone oil at both ends,
(7) The curable resin composition according to (6), characterized by the following (l) to (n):
(L); the polyhydric alcohol compound (c) having two or more hydroxyl groups in the molecule has the structure of the following formula (3),
(M); the compound (d) containing one or more acid anhydride groups in the molecule is at least one selected from the group consisting of the following formulas (4) to (11).
(N); both ends carbinol-modified silicone oil (e) has the structure of the following formula (12),

(Wherein R ₆ and R ₇ each independently represents an alkylene group having 1 to 10 carbon atoms, and m represents an average value of 1 to 1000).

(In the formula, each R ₄ is independently an alkylene group having 1 to 10 carbon atoms or an alkylene group containing an ether bond having 1 to 10 carbon atoms, R ₅ is each independently a methyl group or a phenyl group, and n is an average value. Represents 1 to 1000.)
(8) The near-infrared absorbing dye (C) contains at least one kind selected from a cyanine compound, a polymethine compound, a diimonium compound, a phthalocyanine compound, a naphthalocyanine compound, a metal dithiol complex, and a metal diamine complex. The resin composition according to any one of (1) to (7),
(9) The resin composition according to any one of (1) to (7), wherein the near-infrared absorbing dye (C) is at least one cyanine compound,
(10) The resin composition according to any one of (1) to (7), wherein the cyanine compound according to (9) has 5 or more carbon atoms in the methine chain,
(11) A near-infrared cut filter using the resin composition according to any one of (1) to (10),
(12) An image sensor provided with the near infrared cut filter according to (11),
About.

  According to the present invention, it is possible to provide a near-infrared cut filter having high heat resistance, in particular, a near-infrared cut filter for an image sensor such as a CCD or CMOS, and a resin composition capable of producing them. However, the use of the resin composition of the present invention is not limited to these.

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

  Examples of the epoxy resin (A) used in the present invention 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 complex Cyclic epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, condensates of silicon compounds having epoxy groups with other silicon compounds, polymerizations having epoxy groups And a copolymer of the polymerizable unsaturated compound and other polymerizable unsaturated compound. Among these, a silicone skeleton epoxy resin which is one embodiment of a condensate of a silicon compound having an epoxy group and another silicon compound is preferable from the viewpoints of transparency of the cured product and heat-resistant transparency.

  The silicone skeleton epoxy resin is a resin having an epoxy group having a silicone bond (Si-O bond) as a main skeleton. For example, the silicone skeleton epoxy resin is obtained by polymerizing an epoxy group-containing silicon compound and other silicon compounds. Hydrolysis condensation polymerization products of alkoxysilane compounds having a group and alkoxysilanes having a methyl group or a phenyl group, condensation polymerization products of an alkoxysilane compound having an epoxy group and a silanol-terminated silicone oil, and the like. An addition polymer of a silicone resin having (SiH group) and an epoxy compound having an unsaturated hydrocarbon group such as a vinyl group can also be used.

  As the silicone skeleton epoxy resin in the present invention, a silanol-terminated silicone oil (a) and an epoxy group-containing silicon compound (b) (and optionally an alkoxysilicon compound (f)) are used as raw materials in the following two-stage production. The silicone skeleton epoxy resin obtained through the process is most preferable.

The silanol-terminated silicone oil (a) is a silicone resin represented by the above formula (1) and having silanol groups at both ends, and R _{1 in the} formula (1) is a straight chain having 1 to 10 carbon atoms. A branched, cyclic or cyclic alkyl group, an aryl group having 6 to 14 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. A plurality of R ₁ may be the same or different, but are preferably a phenyl group from the viewpoint of compatibility with other near-infrared absorbing dyes.

  The proportion of the phenyl group present is preferably 0.05 to 2.0 mol, more preferably 0.1 to 1.0 mol, and still more preferably 0.15 to 0.3 mol, per 1 mol of the substituted methyl group. Mol, particularly preferably 0.15 to 0.2 mol. If it is 0.05 mol or less, the composition or the cured product (in the optical filter) has poor compatibility with other raw materials, and if it is 2.0 mol or more, the light resistance (UV resistance) of the cured product (in the optical filter). There are problems such as poor heat cycle resistance.

  In the formula (1), m is an average value calculated in terms of polystyrene and represents 2 to 2000, preferably 3 to 1000, more preferably 3 to 500, and further preferably 3 to 50. When m is 3 or less, the heat cycle resistance of the cured product is inferior, and when m is 200 or more, the mechanical strength of the cured product (optical filter) tends to decrease.

  The weight average molecular weight (Mw) of the silanol-terminated silicone oil (a) is preferably in the range of 400 to 3000 (GPC). When the weight average molecular weight is 400 or less, the properties of the silicone part are difficult to be obtained and the heat resistance and light resistance may be inferior. May be difficult.

As for the molecular weight of the silanol-terminated silicone oil (a) in the present invention, the weight average molecular weight (Mw) was calculated in terms of polystyrene based on the value measured under the following conditions using GPC (gel permeation chromatography). .
GPC measurement conditions Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

  Silanol-terminated silicone oil (a) is obtained by, for example, hydrolyzing and condensing dimethyl dialkoxysilane, methylphenyldichlorosilane, diphenylalkoxysilane, dimethyldichlorosilane, methylphenyldichlorosilane, diphenyldichlorosilane. Can be manufactured.

  Specific examples of the silanol-terminated silicone oil (a) include PRX413 and BY16-873 manufactured by Toray Dow Corning; X-21-5841 and KF-9701 manufactured by Shin-Etsu Chemical Co., Ltd .; XC96-723 manufactured by Momentive. TSR160, YR3370, YF3800, XF3905, YF3057, YF3807, YF3802, YF3897, YF3804, XF3905; FINISH WS 62 M, CT 601M, CT 5000M manufactured by Asahi Kasei Wacker Silicone; DMS-S12 manufactured by Gelest, DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S42, DMS-S45, DMS-S51, PDS-0332, PDS-1615, PDS-9931, etc. are mentioned. Among them, PRX413, BY16-873, X-21-5841, KF-9701, XC96-723, YF3800, YF3804, FINISH WS 62 M, DMS-S12, DMS-S14, DMS-S15, DMS-S21 from the viewpoint of molecular weight. PDS-1615 is preferable, and X-21-5841, XC96-723, YF3800, YF3804, FINISH WS 62 M, DMS-S14, and PDS-1615 are particularly preferable. These silanol-terminated silicone oils (a) may be used alone or in combination of two or more.

  The epoxy group-containing silicon compound (b) is an alkoxy silicon compound represented by the above formula (2). In formula (2), X is not particularly limited as long as X is a substituent having an epoxy group, and specific examples thereof include β-glycidoxyethyl, γ-glycidoxypropyl, γ-glycidoxybutyl and the like. C1-C4 alkyl group substituted with glycidoxy group, glycidyl group, β- (3,4-epoxycyclohexyl) ethyl group, γ- (3,4-epoxycyclohexyl) propyl group, β- (3,4 A cycloalkyl group having 5 to 8 carbon atoms having an oxirane group such as an epoxycycloheptyl) ethyl group, a 4- (3,4-epoxycyclohexyl) butyl group, and a 5- (3,4-epoxycyclohexyl) pentyl group; Examples include substituted alkyl groups having 1 to 5 carbon atoms. Among these, as an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group, an alkyl group having 1 to 3 carbon atoms substituted with a cycloalkyl group having 5 to 8 carbon atoms having an epoxy group, for example, β -Glycidoxyethyl group, γ-glycidoxypropyl group, β- (3,4-epoxycyclohexyl) ethyl group is preferable, and β- (3,4-epoxycyclohexyl) ethyl group is particularly preferable because coloration can be suppressed. Is preferred.

In Formula (2), R ₂ represents an aryl group having a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, phenyl Group, naphthyl group and the like. R2 is preferably a methyl group or a phenyl group from the viewpoint of compatibility and heat-resistant transparency of a cured product (optical filter).

R ₃ in the formula (2) is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. , N-butyl group, i-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group and the like. R3 is preferably a methyl group or an ethyl group, and particularly preferably a methyl group, from the viewpoint of compatibility.

  In formula (2), p represents an integer of 0, 1, 2 and q represents (3-p). From the viewpoint of the mechanical strength of the cured product (optical filter), p is preferably 0 or 1.

  Specific preferred examples of the epoxy group-containing silicon compound (b) include β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxy. Propyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylcyclohexyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylphenyldimethoxysilane, 2- (3 4-D Carboxymethyl) ethyl cyclohexyl dimethoxysilane, and the like, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are particularly preferable. These epoxy group-containing silicon compounds (b) may be used alone or in combination of two or more, and may be used in combination with the alkoxysilicon compound (f) shown below.

  In the silicone skeleton epoxy resin, the alkoxy silicon compound (f) represented by the following formula (13) can be used in combination with the epoxy group-containing silicon compound (b). By using the alkoxysilicon compound (f) in combination, the hardness, gas barrier property, refractive index and the like of the silicone skeleton epoxy resin or the cured product (optical filter) can be adjusted.

In the formula (13), R ₆ and R ₇ are the same as described above, s represents an integer of 0, 1, 2, and 3, and t represents (4-s).

  Specific examples of the alkoxysilicon compound (f) that can be used in combination include methyltrimethoxysilane, phenyltrimethoxysilane, cyclohexyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and diphenyldimethoxy. Silane, diphenyldidiethoxysilane and the like can be mentioned, among which methyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane and diphenyldimethoxysilane are preferable.

  In the present invention, at least one of the silanol-terminated silicone oil (a) and the epoxy group-containing silicon compound (b) (and the alkoxysilicon compound (f) if necessary) used has an aromatic skeleton. From the viewpoint of compatibility with the near-infrared dye, it is preferable to use a compound having a phenyl group. Furthermore, from the viewpoint of workability, the silanol-terminated silicone oil (a) preferably has a phenyl group.

Next, manufacturing steps 1 and 2 will be described.
In the production process 1, the silanol group of the silanol-terminated silicone oil (a) and the alkoxy group of the epoxy group-containing silicon compound (b) (and the alkoxy silicon compound (f) if necessary) are condensed to produce a modified silicone oil ( g).
The production process 2 is a process in which, after the production process 1, water is added to hydrolyze the remaining alkoxy groups to perform condensation.
The method for synthesizing the silicone skeleton epoxy resin in the present invention is carried out through the production steps 1 and 2 described above, and then the modified silicone oil (g) and the epoxy group-containing silicon compound (b) (and the alkoxysilicon compound (f) if necessary). ) Polymerization.

  By dividing the production process into two stages, the silanol group of the silanol-terminated silicone oil (a) and the alkoxy group of the epoxy group-containing silicon compound (b) (and the alkoxysilicon compound (f) as required) reacted. After obtaining the modified silicone oil (g), it is possible to obtain a uniform and stable product by subjecting the remaining alkoxy groups to dealcoholic hydrolysis and condensation.

  When water is added from the beginning as one manufacturing process without making the above manufacturing process into two stages, the condensation reaction between the silanol group and the alkoxy group and the polymerization reaction between the alkoxysilanes become competitive reactions, Due to the difference in the compatibility of the products, a heterogeneous compound is obtained, or a large amount of silanol-terminated silicone oil (a) having no epoxy group remains, which deteriorates the quality of the product.

  The production process 1 is preferably carried out in the presence of a solvent, and alcohols are particularly preferred as the solvent used from the viewpoint of reaction control. Examples of alcohols that can be used include alcohols having 1 to 10 carbon atoms, specifically, methanol, ethanol, propanol, isopropanol, butanol, t-butanol, hexanol, octanol, nonane alcohol, decane alcohol, cyclohexanol, cyclohexane. Examples include pentanol. In the present invention, primary alcohols and secondary alcohols are preferable, and it is particularly preferable to use primary alcohols or a mixture of primary alcohols and secondary alcohols. Examples of primary alcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, nonane alcohol, decane alcohol, propylene glycol and the like, and examples of secondary alcohols include isopropanol, cyclohexanol, Examples include propylene glycol. Moreover, from the problem of removal in post-treatment, alcohols having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, and t-butanol are preferable. These may be used as a mixture. When they are mixed, it is preferable to use at least two selected from primary alcohols and secondary alcohols, and at least one component may contain primary alcohols. From the viewpoint of excellent solubility of the catalyst described later. The amount of primary alcohols used is preferably 5% by weight or more, more preferably 10% by weight or more of the total amount of alcohols.

  By using a secondary alcohol in combination with this reaction, the amount of change in the weight average molecular weight per unit time of the reaction system of production process 1 is smaller than when only the primary alcohol is used, so that the reaction can be controlled. It is easier. In general, in the case of industrial production and the like, it is difficult to strictly control the reaction time and reaction temperature, and therefore the combined use of secondary alcohols is particularly useful for industrial production from the viewpoint of reaction control.

  In the production process 1, the amount of alcohol used is 2% by weight based on the total weight of the silanol-terminated silicone oil (a) and the epoxy group-containing silicon compound (b) (and, if necessary, the alkoxysilicon compound (f)). It is preferable to contain above. More preferably, it is 2 to 100 weight%, More preferably, it is 3 to 50 weight%, Especially preferably, it is 4 to 40 weight%. When the amount is 100% by weight or more, the reaction rate is very low. When the amount is less than 2% by weight, side reaction proceeds, the molecular weight increases, gelation, increase in viscosity, increase in elastic modulus, The problem that it becomes difficult to use is generated.

  In this reaction, other solvents may be used in combination as necessary. Examples of solvents that can be used in combination include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone; esters such as ethyl acetate, butyl acetate, ethyl lactate, and isopropyl butanoate; hydrocarbon compounds such as hexane, cyclohexane, toluene, and xylene Etc. can be illustrated.

  The reaction in the production process 1 is preferably performed in the presence of a catalyst in order to improve the reaction efficiency. As the catalyst to be used, any compound showing acidity or basicity can be used. Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, acetic acid and oxalic acid. Examples of the basic catalyst include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide; alkalis such as sodium carbonate, potassium carbonate, sodium hydrogencarbonate and potassium hydrogencarbonate. Examples include inorganic bases such as metal carbonates; organic bases such as ammonia, triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide. Among these, a basic catalyst is particularly preferred, and a base such as an alkali metal salt such as sodium hydroxide, potassium hydroxide or calcium hydroxide, or an alkaline earth metal salt is preferred in order to facilitate removal of the catalyst from the product. Are preferred, and alkali metal or alkaline earth metal hydroxides are particularly preferred. The amount of the catalyst added is usually 0.001 to 5% by weight based on the total weight of the silanol-terminated silicone oil (a) and the epoxy group-containing silicon compound (b) (and, if necessary, the alkoxysilicon compound (f)). Preferably, it is 0.01 to 2% by weight. In addition, the catalyst is preferably added directly or dissolved in advance in an alcohol solvent such as methanol, ethanol, propanol, or butanol.

  In this reaction, if water is present even in a small amount, the sol-gel reaction other than the target reaction proceeds competitively, and the alkoxy group-containing silicon compound (b) (and the alkoxy silicon compound (f) if necessary) alkoxy Since the reaction product produced by the polycondensation reaction of the group and the silanol-terminated silicone oil (a) are incompatible with each other and become cloudy, the allowable range of moisture in this reaction is that the silanol-terminated silicone oil (a) and the epoxy group contain It is 0.5% by weight or less, more preferably 0.3% by weight or less, based on the total weight of the silicon compound (b) (and, if necessary, the alkoxysilicon compound (f)), and anhydrous conditions are particularly preferred.

  Although the reaction temperature of the manufacturing process 1 is based also on a catalyst amount and a use solvent, it is 20-160 degreeC normally, Preferably it is 40-100 degreeC, Most preferably, it is 50-95 degreeC. The reaction time is usually 1 to 20 hours, preferably 3 to 12 hours.

  Thus, it is thought that the modified silicone oil (g) obtained by the manufacturing process 1 has a compound of following formula (14) as a main component.

In formula (14), R ₁ and m have the same meaning as described above. R ₈ represents any one of the aforementioned X, R ₆ , and —OR ₇ , and R ₉ represents R ₆ and / or —OR ₇ , respectively.

Next, the manufacturing process 2 will be described.
After completion of the reaction in the production step 1, water is added to carry out polymerization (sol-gel reaction) between the alkoxy groups remaining in the obtained modified silicone oil (g). Under the present circumstances, you may add the silicon compound (b) (and alkoxy silicon compound (f) as needed) and a catalyst which contain the above-mentioned epoxy group within the range of the above-mentioned as needed. This reaction is performed between (1) the modified silicone oils (a) and / or (2) the silicon compound (b) containing an epoxy group (and, if used, the alkoxysilicon compound (f)). And / or (3) a silicon compound (b) containing an epoxy group (and an alkoxysilicon compound (f) if used) and / or (4) a silicon compound containing an epoxy group (b ) (And the alkoxysilicon compound (f), if used) is a step of performing a polymerization reaction between the partially polymerized silicone oil (g). The above polymerization reactions (1) to (4) are considered to proceed simultaneously.
In the production process 2, as described above, a basic inorganic catalyst is preferable as the catalyst, and a necessary amount in the stage of the production process 1 may be added in advance.

  In the production process 2, it is preferable to add a solvent. The solvent used in the production process 2 is preferably the same alcohol as in the production process 1. Examples of alcohols that can be used include alcohols having 1 to 10 carbon atoms, specifically, methanol, ethanol, propanol, isopropanol, butanol, t-butanol, hexanol, octanol, nonane alcohol, decane alcohol, cyclohexanol, cyclohexane. Examples include pentanol. In particular, primary alcohols and secondary alcohols are preferable, and primary alcohols are particularly preferable. In consideration of removal of the solvent after the reaction, low-molecular-weight alcohols having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, and t-butanol are preferable. These alcohols may be used as a mixture of two or more. By using these alcohols, the molecular weight can be stably controlled. The addition amount of alcohols in the production process 2 is 20 to 20 based on the total weight of the silanol-terminated silicone oil (a) and the silicon compound (b) containing an epoxy group (and the alkoxysilicon compound (f) if necessary). It is 200% by weight, preferably 20 to 150% by weight, particularly preferably 30 to 120% by weight.

  As the water to be added in the production process 2, any of ion-exchanged water, distilled water and clean water can be used. The usage-amount of water is 0.5-8.0 equivalent with respect to the amount of remaining alkoxy groups, More preferably, it is 0.6-5.0 equivalent, Most preferably, it is 0.65-2.0 equivalent. When the amount of water is less than 0.5 equivalent, the reaction rate decreases, and the silicon compound (b) containing unreacted epoxy groups (and the alkoxysilicon compound (f) if necessary) remains, and the resin Problems such as poor curing of the composition may occur. On the other hand, if it exceeds 8.0 equivalents, it is difficult to control the molecular weight and the stability of the silicone skeleton epoxy resin may be hindered.

  The reaction temperature in production step 2 is usually 20 to 160 ° C, preferably 40 to 100 ° C, particularly preferably 50 to 95 ° C, although it depends on the amount of catalyst and the solvent used. The reaction time is usually 1 to 20 hours, preferably 3 to 12 hours.

  After completion of the reaction, water or the like is added to the reaction solution to stop the reaction and the reaction product is washed with water to remove the catalyst. When washing with water, it is preferable to add a solvent capable of phase separation with water if necessary. Preferred solvents include, for example, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone; esters such as ethyl acetate, butyl acetate, ethyl lactate and isopropyl butanoate; hydrocarbons such as hexane, cyclohexane, toluene and xylene, Etc.

  In this reaction, the catalyst may be removed only by washing with water, but since the reaction is carried out under either acidic or basic conditions, the reaction product is washed with water after stopping the reaction by neutralization or adsorbed. The adsorbent can be removed by filtration after adsorbing the catalyst using the adsorbent. An acidic or basic compound can be used for the neutralization reaction. Examples of the acidic compound include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, acetic acid and oxalic acid. Examples of basic compounds include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide; alkali metals such as sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate. Carbonates; inorganic bases such as phosphates such as phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, polyphosphoric acid, sodium tripolyphosphate; ammonia, triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, tri Organic bases such as ethanolamine and tetramethylammonium hydroxide can be used. Among these, an inorganic base or an inorganic acid that can be easily removed from the product is preferable, and phosphates that can easily adjust the pH to near neutral are more preferable.

  Examples of the adsorbent include activated clay, activated carbon, zeolite, inorganic / organic synthetic adsorbent, ion exchange resin, and the like, and specific examples include the following products. As the activated clay, for example, activated clay SA35, SA1, T, R-15, E, Nikkanite G-36, G-153, G-168 manufactured by Toshin Kasei Co., Ltd., Galeon manufactured by Mizusawa Chemical Industry Co., Ltd. Earth, Mizuka Ace, etc. are listed. Examples of the activated carbon include CL-H, Y-10S, and Y-10SF manufactured by Ajinomoto Fine Techno; S, Y, FC, DP, SA1000, K, A, KA, M, manufactured by Phutamura Chemical Co., Ltd. Examples thereof include CW130BR, CW130AR, and GM130A. Examples of zeolite include molecular sieves 3A, 4A, 5A, and 13X manufactured by Union Showa. As a synthetic adsorbent, for example, Kyoward 100, 200, 300, 400, 500, 600, 700, 1000, 2000 manufactured by Kyowa Chemical Co., Ltd .; Amberlyst 15JWET, 15DRY, 16WET manufactured by Rohm and Haas 31WET, A21, Amberlite IRA400JCl, IRA403BLCl, IRA404JCl; Dowex 66, HCR-S, HCR-W2, MAC-3, etc., manufactured by Dow Chemical. These adsorbents are added to the reaction solution, stirred, heated, and so on. After adsorbing the catalyst, the adsorbent is filtered and the residue is washed with water to remove the catalyst and adsorbent.

  After completion of the reaction, it can be purified by a general separation and purification method in addition to washing with water and filtration. Examples of the purification method include column chromatography, concentration under reduced pressure, distillation, extraction and the like. These purification methods may be performed alone or in combination. When the reaction is carried out using a solvent in which water is mixed with the reaction solvent in advance, the reaction solvent containing water is removed from the system by distillation or concentration under reduced pressure after the completion of the reaction, and then washed with a solvent that can be separated from water. Is preferred. After washing with water, the silicone skeleton epoxy resin of the present invention can be obtained by removing the solvent by vacuum concentration or the like.

In the following, silanol-terminated silicone oil (a) and silicon compound (b) containing an epoxy group, which is a preferred embodiment of the silicone skeleton epoxy resin in the present invention, obtained through the above-mentioned production process 1 and production process 2 ( And the condensate with an alkoxy silicon compound (f)) is demonstrated as needed. The silicone skeleton epoxy resin of the present invention is a liquid compound which is usually colorless and transparent and has fluidity at 25 ° C. The molecular weight is preferably 800 to 10,000, more preferably 1000 to 5000, and particularly preferably 1500 to 2800 as the weight average molecular weight measured by GPC. When the weight average molecular weight is 800 or less, the heat resistance decreases, and when it is 5000 or more, the optical filter produced on the substrate may be peeled off from the substrate during curing. The weight average molecular weight (Mw) was calculated by polystyrene conversion measured under the following conditions using GPC (gel permeation chromatography).
GPC measurement conditions Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

  The epoxy equivalent (measured by the method described in JIS K-7236) of the silicone skeleton epoxy resin is preferably 300 to 1500 g / eq, more preferably 320 to 1400 g / eq, further preferably 350 to 1200 g / eq, and 350 to 1000 g / eq. eq is particularly preferred. On the other hand, when the epoxy equivalent is 300 g / eq or less or 1500 g / eq or more, the mechanical properties of the cured product may be deteriorated.

  The silicone skeleton epoxy resin may be a single silicone skeleton epoxy resin or a mixture of two or more silicone skeleton epoxy resins. Here, from the viewpoint of appropriate mechanical strength of the cured product, even if it is a single silicone skeleton epoxy resin or a mixture of two or more silicone skeleton epoxy resins, the epoxy equivalent of a specific silicone skeleton epoxy resin × The epoxy equivalent of (content of the specific silicone skeleton epoxy resin / total amount of silicone skeleton epoxy resin) is preferably 300 to 1500 g / eq, and particularly preferably 350 to 1000 g / eq.

In the silicone skeleton epoxy resin, the ratio of silicon atoms to which three oxygen atoms are bonded to the total silicon atoms can be determined by ¹ H-NMR, ²⁹ Si-NMR, elemental analysis, etc. Preferably, 5-40 mol% is more preferable, and especially 6-35 mol% is preferable. When the ratio of silicon atoms bonded to three oxygen atoms derived from silsesquioxane with respect to all silicon atoms is less than 3 mol%, the cured product becomes very soft, and surface tack and scratches tend to be easily formed, resulting in 50 mol%. Exceeding this causes a problem that the cured product is extremely cured.

  As the silicone skeleton epoxy resin, the above silanol-terminated silicone oil (a) is not used, but is a condensation polymer of an epoxy group-containing silicon compound (b) (and, if necessary, an alkoxysilicon compound (f)). There may be.

  This compound can be produced by a one-step reaction, and includes a silicon compound (b) containing an epoxy group represented by the above formula (2) (and, if necessary, represented by the above formula (13). In the same manner, an appropriate amount of water is added dropwise to the alkoxysilicon compound (f)) in the presence of a catalyst or a solvent, and condensed under the conditions of a reaction temperature of 40 to 100 ° C. and a reaction time of 1 to 24 hours. A condensate of the silicon compound (b) containing an epoxy group (and, if necessary, the alkoxysilicon compound (f)) can be obtained by post-treatment such as inactivation or removal of the catalyst.

  In the thermosetting resin composition of the present invention, other epoxy resins may be used alone or in combination with the above-described silicone skeleton epoxy resin. Epoxy resins that can be used in combination include epoxy resins that are glycidyl etherification products of phenolic compounds, epoxy resins that are glycidyl etherification products of various novolak resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, and glycidyl esters. Epoxy resins, glycidylamine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, copolymers of polymerizable unsaturated compounds having an epoxy group and other polymerizable unsaturated compounds, etc. . These epoxy resins may be used alone or in combination of two or more.

  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, phloroglicinol, diisopropyl Examples include phenols having a redene skeleton; phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene; epoxy resins that are glycidyl etherified products of polyphenol compounds such as phenolized polybutadiene, and the like.

  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 composed 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 the epoxy resin obtained by glycidylation of the halogenated phenols include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolak, 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 another polymerizable unsaturated compound other than that, Marproof G-0115S, G-0130S, G-0250S manufactured by NOF Corporation are available. G-1010S, G-0150M, G-2050M and the like, and examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, 4-vinyl-1-cyclohexene-1 , 2-epoxide and the like. Examples of other polymerizable unsaturated compound copolymers include methyl (meth) acrylate, ether (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, and vinylcyclohexane.

  Among the above-mentioned epoxy resins, from the viewpoint of transparency, heat-resistant transparency, and light-resistant transparency, the combined use of an alicyclic epoxy resin is preferable, a compound having an epoxycyclohexane structure in its skeleton is preferable, and an oxidation of a compound having a cyclohexene structure Epoxy resins obtained by reaction are particularly preferred.

  Examples of these epoxy resins include esterification reaction of cyclohexene carboxylic acid and alcohols described in Non-Patent Documents 1 and 2 (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980)) or cyclohexene. Esterification reaction between methanol and carboxylic acids, or Tyschenko reaction of cyclohexene aldehyde described in Patent Documents 4 and 5 (Japanese Patent Laid-Open Nos. 2003-170059 and 2004-262871), and further Patent Document 6 (Japanese Patent Laid-Open No. 2006-2006). No. 052187) and the like, which are obtained by oxidizing a compound that can be produced by a transesterification reaction of a cyclohexenecarboxylic acid ester (the entire contents of these references are incorporated herein by reference).

  The alcohol used in these synthesis examples is not particularly limited as long as it is a compound having an alcoholic hydroxyl group. For example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4 -Butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tri Diols such as cyclodecane dimethanol and norbornenediol; Triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol; pentaerythritol, ditrimethylo Such as tetraols such as propane. Examples of carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid. Furthermore, the acetal compound by the acetal reaction of a cyclohexene aldehyde derivative and alcohol is mentioned.

  Specific examples of these epoxy resins include ERL-4221, UVR-6105, ERL-4299 manufactured by Dow Chemical; Celoxide 2021P manufactured by Daicel Chemical Industries, Epolide GT401, EHPE3150, EHPE3150CE; dicyclopentadiene diepoxide, and the like. However, it is not limited to these (reference: review epoxy resin basic edition I p76-85, the whole content is taken in here as a reference).

  When the silicone skeleton epoxy resin and another epoxy resin are used in combination, the ratio of the silicone skeleton epoxy resin is preferably 60 to 99 parts by weight, and 90 to 97 parts by weight with respect to the total weight of all the epoxy resins. Is particularly preferred. If it is less than 60 parts by weight, the light resistance (UV resistance) of the cured product may be inferior.

  In the curable resin composition of the present invention, the blending ratio of the epoxy resin curing agent (B) to all the epoxy resins including the silicone skeleton epoxy resin is 0.5 to 1 with respect to 1 equivalent of the epoxy groups of all the epoxy resins. It is preferred to use 2 equivalents of curing agent. If it is less than 0.5 equivalent or more than 1.2 equivalent to 1 equivalent of epoxy group, good cured properties may not be obtained.

Next, the epoxy resin curing agent (B) will be described.
Examples of the epoxy resin curing agent (B) used in the present invention include amine compounds, acid anhydride compounds, amide compounds, phenolic compounds, and polyvalent carboxylic acids, but hardness, workability (room temperature) In particular, acid anhydrides and polyvalent carboxylic acids are preferable from the viewpoint of transparency of the cured product, and among them, both terminal carbinol-modified silicone oils (e) described later, The polyhydric alcohol compound (c) having the above hydroxyl group, the compound (d) having one carboxylic anhydride group in the molecule, and the compound having two or more carboxylic anhydride groups in the molecule (if necessary) ( Most preferred are polyvalent carboxylic acid resins obtained by addition reaction with h).

  Specific examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydro anhydride Phthalic acid, methylhexahydrophthalic anhydride, glutaric anhydride, 2,4-diethyl glutaric anhydride, 3,3-dimethyl glutaric 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, and the like. . 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 Are preferable from the viewpoints of light resistance, transparency, and workability.

  The polyvalent carboxylic acid is a compound having at least two carboxyl groups, and is preferably a bifunctional to hexafunctional carboxylic acid, for example, butanedioic acid, pentanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid. Linear alkyl diacids such as acid, decanedioic acid and malic acid; alkyltricarboxylic acids such as 1,3,5-pentanetricarboxylic acid and citric acid; phthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid Aliphatic cyclic polycarboxylic acids such as acid, methyltetrahydrophthalic acid, cyclohexanetricarboxylic acid, nadic acid, and methylnadic acid; multimers of unsaturated fatty acids such as linolenic acid and oleic acid; and dimer acids that are reduced products thereof; Compounds obtained by reaction of 2-6 functional polyhydric alcohol and acid anhydride, etc. The recited, compounds obtained by the reaction of polyhydric alcohols and anhydrides of 2-6 functionalities are refractory, and more preferable from the viewpoint of workability. Furthermore, the polyhydric carboxylic acid whose said acid anhydride is a saturated aliphatic cyclic acid anhydride is especially preferable from a transparency viewpoint.

  The 2- to 6-functional polyhydric alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol. 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecanedi Diols such as methanol and norbornenediol; Triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol; Teto such as pentaerythritol and ditrimethylolpropane Ols; hexaols such as dipentaerythritol, and the like.

  Preferred polyhydric alcohols are alcohols having 5 or more carbon atoms, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 2, Compounds such as 4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornenediol are preferable, and among them, 2-ethyl-2-butyl-1, Alcohols having a branched chain structure or cyclic structure such as 3-propanediol, neopentyl glycol, 2,4-diethylpentanediol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, norbornenediol are heat resistant. From the viewpoint of transparency, In particular, tricyclodecane dimethanol is preferable.

  Examples of acid anhydrides to be reacted with polyhydric alcohol include methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, glutaric anhydride, and 2,4-diethylglutaric anhydride. Acid, 3,3-dimethyl glutaric anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2, 3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and the like are preferable, and among them, methylhexahydrophthalic anhydride, 2,4-diethyl glutaric anhydride, cyclohexane-1,3 , 4-tricarboxylic acid-3,4-anhydride is preferred from the viewpoints of heat resistance, transparency and workability. Even if it is a well-known method as conditions for addition reaction, it can be used without limitation, for example, an acid anhydride and a polyhydric alcohol are reacted at 40 to 150 ° C. under non-catalytic and solvent-free conditions, After completion of the reaction, it can be easily obtained by taking it out as it is.

  From here, the both-terminal carbinol-modified silicone oil (e), the polyhydric alcohol compound (c) having two or more hydroxyl groups in the molecule, and two in the molecule, which are raw materials for the polyvalent carboxylic acid resin The compound (e) having the above acid anhydride group and the compound (h) having one acid anhydride group in the molecule will be described.

Both end carbinol-modified silicone oil (e) is a silicone compound having an alcoholic hydroxyl group at both ends represented by the above formula (12). In the formula (12), R ₄ each independently represents an alkylene group having 1 to 10 carbon atoms or an alkylene group containing an ether bond having 1 to 10 carbon atoms, R ₅ each independently represents a methyl group or a phenyl group, n represents an average value of 1-1000.

Specific examples of R _{4 in} the formula (12) include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, isopentylene, hexylene, heptylene, octylene and other alkylene groups; ethoxyethylene group, propoxyethylene group propoxypropylene And an alkylene group having an ether bond such as an ethoxypropylene group. Particularly preferred are propoxyethylene group and ethoxypropylene group.

  In formula (12), n is an average value of 1 to 1000, preferably 2 to 100, more preferably 5 to 30.

  The both-end carbinol-modified silicone oil (e) represented by the formula (12) is, for example, Shin-Etsu Chemical Co., Ltd. X-22-160AS, KF6001, KF6002, KF6003; Toray Dow Corning Co., Ltd. BY16 -201, BY16-004, SF8427; XF42-B0970, XF42-C3294 manufactured by Momentive Performance Materials Japan GK; IM11, IM15 manufactured by Asahi Kasei Wacker Silicone Co., Ltd .; FM- manufactured by JNC Corporation 4411, FM-4421, etc., all of which are available from the market. These two terminal carbinol-modified silicone oils may be used alone or in combination of two or more. Among these, X-22-160AS, KF6001, KF6002, BY16-201, XF42-B0970, and FM4411 are preferable.

  Examples of the polyhydric alcohol compound (c) having two or more hydroxyl groups in the molecule include a terminal alcohol polyester compound (i), a hydrocarbon polyhydric alcohol compound (j), and a terminal alcohol polycarbonate compound.

  Although it does not specifically limit as terminal alcohol polyester compound (i), For example, the polyester compound etc. which have a hydroxyl group at the terminal shown by the said Formula (3) are mentioned.

In the formula (3), specific examples of R ₆ include linear alkylene groups having 1 to 10 carbon atoms such as ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene; isopropylene, ethylbutylpropylene, isobutylene, Examples thereof include alkylene groups having a branched chain of 1 to 10 carbon atoms such as isopentylene, neopentylene, diethylpentylene, etc .; alkylene groups having a cyclic structure such as cyclopentanedimethylene, cyclohexanedimethylene, and the like. Among these, an alkylene group having a branched chain having 1 to 10 carbon atoms or an alkylene group having a cyclic structure is preferable, and in particular, ethylbutylpropylene, isobutylene, neopentylene, diethylpentylene, cyclohexanedimethylene is a heat-resistant transparency of a cured product. It is preferable from the viewpoint.

In formula (3), specific examples of R ₇ include linear alkylene groups having 1 to 10 carbon atoms such as ethylene, propylene, butylene, pentylene, hexylene, heptylene, and octylene; isopropylene, ethylbutylpropylene, and isobutylene. , An alkylene group having a branched chain of 1 to 10 carbon atoms such as isopentylene, neopentylene and diethylpentylene; an alkylene group having a cyclic structure such as clopentanedimethylene and cyclohexanedimethylene. Among these, a linear alkylene group having 1 to 10 carbon atoms is preferable, and propylene, butylene, pentylene, and hexylene are particularly preferable from the viewpoint of adhesion of a cured product to a substrate.

  In formula (3), m is an average value of 1 to 1000, preferably 1 to 300, more preferably 2 to 100, and further preferably 3 to 30.

Although the weight average molecular weight (Mw) of terminal alcohol polyester compound (i) is 500-50000, Preferably it is 500-10000, More preferably, it is 500-3000. When the weight average molecular weight is less than 500, the cured product hardness of the curable resin composition of the present invention becomes very high, cracks occur in a heat cycle test or the like, and when the weight average molecular weight is more than 50000, the cured product becomes sticky. There are problems that occur. In the present invention, the weight average molecular weight (Mw) was calculated in terms of polystyrene using GPC (gel permeation chromatography) based on the values measured under the following conditions.
GPC measurement conditions Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

  Examples of the terminal alcohol polyester compound (i) represented by the formula (3) include polyester polyols having an alcoholic hydroxyl group at the terminal. Specific examples thereof are polyester polyols, Kyowa Pole Chemical Co., Ltd. Kyowapol 1000PA, 2000PA, 3000PA, 2000BA; Adeka New Ace Y9-10, YT-101; Daicel Plaxel 220EB, 220EC manufactured by Chemical Industry Co., Ltd .; Polylite OD-X-286, OD-X-102, OD-X-355, OD-X-2355, OD-X-2330, OD- manufactured by DIC Corporation X-240, OD-X-668, OD-X-2554, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X -2068, OD-X-2547, OD-X-2420, OD-X-2523, OD-X-2555; HS2 manufactured by Toyokuni Oil Co., Ltd. -201AP, HS2H-351A, HS2H-451A, HS2H-851A, HS2N-221A, HS2N-521A, HS2H-220S, HS2N-220S, HS2N-226P, HS2B-222A, HOKOKOOL HT-110, HT-210, Examples thereof include HT-12, HT-250, HT-310, and HT-40M, all of which are available from the market. These polyester compounds can be used alone or in combination of two or more. Among these, Kyowapol 1000PA, Adeka New Ace Y9-10, and HS2N-221A are preferable.

  The hydrocarbon polyhydric alcohol compound (j) is a hydrocarbon compound having two or more hydroxyl groups in the molecule, such as ethylene glycol, propylene glycol, propanediol, butanediol, dimethylethanol, pentanediol, neopentyl glycol, Hexanediol, dimethylbutanediol, heptanediol, dimethylpentanediol, diethylpropanediol, octanediol, dimethylhexanediol, diethylbutanediol, nonanediol, dimethylheptanediol, diethylpentanediol, decanediol, dimethyloctanediol, diethylhexanediol , Ethylbutylpropanediol, 3-methylol-1,5-pentanediol, diglycerin, dipentaerythritol, tri Chain hydrocarbon polyhydric alcohol compounds such as tyrolpropane and ditrimethylolpropane; cyclopentanediol, cyclopentanedimethanol, cyclohexanediol, cyclohexanedimethanol, tricyclodecanediol, tricyclodecane dimethanol, norbornanediol, norbornane dimethanol Cyclic hydrocarbon polyhydric alcohol compounds such as: heterocyclic polyhydric alcohol compounds such as tris (2-hydroxyethyl) isocyanurate and trishydroxymethyl isocyanurate, and the like. These hydrocarbon polyhydric alcohol compounds (j) may be used alone or in admixture of two or more. Among these, tricyclodecane dimethanol, ditrimethylolpropane, diglycerin, and cyclohexanedimethanol are preferable from the viewpoints of the strength of the cured product and the transparency of the cured product.

  Although the usage-amount of the polyhydric alcohol compound (c) which has a 2 or more hydroxyl group in a molecule | numerator is not specifically limited, Preferably it is 0.5-200 with respect to 100 weight part of both terminal carbinol modified silicone oil (e). Parts by weight, more preferably 5 to 50 parts by weight, still more preferably 10 to 30 parts by weight. 0.5 parts by weight or more is preferable because the mechanical strength of the cured product is further improved, and 200 parts by weight or less is more preferable because the heat-resistant transparency of the cured product is further improved.

  Next, the compound (d) having one carboxylic acid anhydride group in the molecule includes succinic acid anhydride, methyl succinic acid anhydride, ethyl succinic acid anhydride, 2,3-butanedicarboxylic acid anhydride, 2,4-pentane. Saturated aliphatic carboxylic acid anhydrides such as dicarboxylic acid anhydride and 3,5-heptanedicarboxylic acid anhydride; unsaturated aliphatic carboxylic acid anhydrides such as maleic acid anhydride and dodecyl succinic acid anhydride, hexahydrophthalic acid anhydride , Methylhexahydrophthalic anhydride, 1,3-cyclohexanedicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, nadic acid anhydride, methylnadic Acid anhydride, bicyclo [2,2,2] octane-2,3-dicarboxylic acid anhydride, 1,2,4-cyclohexanetricarboxylic acid- , 2-anhydride, glutaric anhydride, 2,4-diethyl glutaric anhydride, 3,3-dimethyl glutaric anhydride and other cyclic saturated aliphatic carboxylic anhydrides; tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride , Nadic acid anhydride, methyl nadic acid anhydride, 4,5-dimethyl-4-cyclohexene-1,2-dicarboxylic acid anhydride, bicyclo [2.2.2] -5-octene-2,3-dicarboxylic acid And cyclic unsaturated aliphatic carboxylic anhydrides such as anhydrides; aromatic carboxylic anhydrides such as phthalic anhydride, isophthalic anhydride, terephthalic anhydride, trimellitic anhydride, and the like. Among them, a cured product obtained by curing a polyvalent carboxylic acid resin and an epoxy resin has excellent transparency, such as hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, and glutaric anhydride. 2,4-diethyl glutaric anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride. preferable. Of these, methylhexahydrophthalic anhydride and 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride are more preferable, and methylhexahydrophthalic anhydride and 2,4-diethylglutaric anhydride are particularly preferable. One carboxylic anhydride group in the molecule may be used as the compound (d), or two or more kinds may be used in combination.

  The compound (h) having two or more carboxylic acid anhydride groups in the molecule is, for example, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid. Dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, pyromellitic anhydride, 5- (2,5- Dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene- 1,2-dicarboxylic anhydride and the like. Especially, since the transparency of the cured product obtained by curing the polyvalent carboxylic acid resin and the above-described epoxy resin is excellent, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,4,5 -Cyclohexanetetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride is preferred, 2,3,4-butanetetracarboxylic dianhydride is preferred. The compound (h) having two or more carboxylic acid anhydride groups in the molecule may be used alone or in combination of two or more.

  The amount of the compound (h) having two carboxylic anhydride groups in the molecule is preferably 5 to 1000 parts by weight with respect to 100 parts by weight of the compound (d) having one carboxylic anhydride group in the molecule. Is 10 to 500 parts by weight, more preferably 15 to 300 parts by weight. If it is larger than 300 parts by weight, the polyvalent carboxylic acid resin may be too high in molecular weight and workability may be inferior.

  Both ends carbinol-modified silicone oil (e), polyhydric alcohol compound (c) having two or more hydroxyl groups in the molecule, compound (d) having one carboxylic anhydride group in the molecule, two in the molecule The amount of the compound (h) having one or more carboxylic anhydride groups is the total alcohol of the carbinol-modified silicone oil (e) at both ends and the polyhydric alcohol compound (c) having two or more hydroxyl groups in the molecule. Total carboxylic acid anhydride group of the compound (d) having one carboxylic acid anhydride group in the molecule and the compound (h) having two or more carboxylic acid anhydride groups in the molecule with respect to 1 equivalent of the functional hydroxyl group Is preferably 0.5 to 2.0 equivalents, more preferably 0.8 to 1.5 equivalents. If it is 0.5 equivalent or more, it is preferable because the mechanical strength of the cured product is good, and if it is 2.0 equivalent or less, a large amount of carboxylic acid anhydride groups do not remain and storage stability becomes good.

  The production of the polyvalent carboxylic acid resin can be performed in a solvent or without a solvent. Solvents used include: carbinol-modified silicone oil (e) at both ends, polyhydric alcohol compound (c) having two or more hydroxyl groups in the molecule, compound having one or more carboxylic anhydride groups in the molecule (D) The compound (h) having two or more carboxylic anhydride groups in the molecule and a solvent that does not react with each can be used without particular limitation. Examples of solvents that can be used include aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, and acetonitrile; ketones such as methyl ethyl ketone, cyclopentanone, and methyl isobutyl ketone; and aromatic hydrocarbons such as toluene and xylene. Among these, aromatic hydrocarbons and ketones are preferable. These solvents may be used alone or in combination of two or more. In the case of using a solvent, the amount used is carbinol-modified silicone oil (e) at both ends, polyhydric alcohol compound (c) having two or more hydroxyl groups in the molecule, one or more carboxylic acid anhydrides in the molecule. 0.5 to 300 parts by weight is preferred with respect to 100 parts by weight in total of the compound (d) having a group and the compound (h) having two or more carboxylic anhydride groups in the molecule when used.

  The polyvalent carboxylic acid resin can be produced with or without a catalyst. Examples of the catalyst used include acidic compounds such as hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, nitric acid, trifluoroacetic acid, and trichloroacetic acid; sodium hydroxide, potassium hydroxide, calcium hydroxide, water Metal hydroxides such as magnesium oxide; amine compounds such as triethylamine, tripropylamine, tributylamine; pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, imidazole, triazole, Heterocyclic compounds such as tetrazole; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide Trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium Quaternary ammonium salts such as acetate; orthotitanates such as tetraethyl orthotitanate and tetramethyl orthotitanate; tin octylate, cobalt octylate, zinc octylate, manganese octylate, calcium octylate, sodium octylate, octylic acid And metal soaps such as potassium. One type of catalyst may be used, or two or more types may be mixed and used.

  The amount of the catalyst used is as follows: carbinol-modified silicone oil (e) at both ends, polyhydric alcohol compound (c) having two or more hydroxyl groups in the molecule, compound having one carboxylic anhydride group in the molecule (d ), When used, 0.05 to 10 parts by weight is preferable with respect to 100 parts by weight in total of the compound (h) having two or more carboxylic anhydride groups in the molecule. The catalyst may be added directly or dissolved or dispersed in advance in a solvent or the like. However, when alcohols such as methanol and ethanol and water are used as the solvent, unreacted one carboxylic acid in the molecule is added. Since it reacts with the compound (d) having an acid anhydride group and the compound (h) having two or more carboxylic anhydride groups in the molecule, it is preferable to avoid it.

  The reaction temperature during the production of the polycarboxylic acid resin is usually 20 to 160 ° C., preferably 50 to 150 ° C., particularly preferably 60 to 145 ° C., although it depends on the amount of catalyst and the solvent used. The reaction time is usually 1 to 20 hours, preferably 3 to 12 hours. The reaction may be carried out in two or more stages, for example, after reacting at 20 to 100 ° C. for 1 to 8 hours, it may be allowed to react at 100 to 160 ° C. for 1 to 12 hours. In particular, the compound (d) having one carboxylic acid anhydride group in the molecule is often highly volatile, and when such a compound is used, it is reacted at 20 to 100 ° C. in advance and then 100 to 160. By reacting at ℃, volatilization can be suppressed. Thereby, not only can the diffusion of harmful substances into the atmosphere be suppressed, but a polyvalent carboxylic acid resin as designed can be obtained.

In the case of production using a catalyst, the catalyst can be removed by deactivating the catalyst and / or washing with water as necessary, but it is left as it is, and the curable resin composition of the present invention is cured. It can also be used as an accelerator. When performing the water washing treatment, it is preferable to add a solvent capable of phase separation with water depending on the type of the solvent used. Examples of solvents used in combination include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone; esters such as ethyl acetate, butyl acetate, ethyl lactate and isopropyl butanoate; hydrocarbons such as hexane, cyclohexane, toluene and xylene , Etc.
When a solvent is used for the reaction or washing with water, it can be removed by ordinary vacuum concentration treatment.

The polyvalent carboxylic acid resin thus obtained is normally a liquid having fluidity at 25 ° C. The molecular weight is preferably 800 to 80000, more preferably 1000 to 10000, and particularly preferably 1500 to 8000 as the weight average molecular weight measured by GPC. When the weight average molecular weight is less than 800, the fluidity at 25 ° C. decreases, and when it exceeds 80000, the compatibility with the epoxy resin described later may be inferior when a curable resin composition is used. There is.
The weight average molecular weight (Mw) was calculated in terms of polystyrene measured using GPC (gel permeation chromatography) under the following conditions.
GPC measurement conditions Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

  The acid value (measured by the method described in JIS K-2501) of the manufactured polycarboxylic acid resin is preferably 35 to 200 mgKOH / g, more preferably 50 to 180 mgKOH / g, and particularly preferably 60 to 150 mgKOH / g. When the functional group equivalent is less than 35 mgKOH / g or more than 150 mgKOH / g, the cured product tends to be extremely cured, and the mechanical properties of the cured product tend to deteriorate, which is not preferable.

  In the curable resin composition of the present invention, two or more acid anhydrides, polyvalent carboxylic acids, and polyvalent carboxylic acid resins may be used in combination. When used in combination, the acid anhydride and / or the polyvalent carboxylic acid resin can be used at a ratio of 0.5 to 99.5% by weight of the total of the epoxy resin curing agent.

  In the case where a curing agent other than the above-mentioned acid anhydride and / or polyvalent carboxylic acid resin and / or polyvalent carboxylic acid resin is used in combination as the epoxy resin curing agent, the acid anhydride and / or polyvalent carboxylic acid and / or polyhydric carboxylic acid are used. The proportion of the total amount of the polyvalent carboxylic acid resin in the total curing agent is preferably 30% by weight or more, particularly preferably 40% by weight or more.

  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 and polyamide compounds (diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from ethylenediamine and dimer of linolenic acid, etc.) Polyphenols (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-hydroxyphenyl) 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′-bis (chloro Methyl) benzene, polycondensates with 1,4′-bis (methoxymethyl) benzene and their modified products, halogenated bisphenols such as tetrabromobisphenol A, and condensation of terpenes and phenols Products, others (imidazole, trifluoroborane-amine complex, guanidine derivatives, etc.), etc., but are not limited to these, and these may be used alone or in combination of two or more. .

  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. The coupling agent is added in an amount of usually 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, if necessary, with respect to 100 parts by weight of the curable resin composition of the present invention.

  In the curable resin composition of the present invention, it is possible to supplement mechanical strength and the like without impairing transparency by using a nano-order level inorganic filler as necessary. Thus, the average particle diameter of the nano-order level inorganic filler used for ensuring transparency is preferably 500 nm or less, and particularly preferably 200 nm or less. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These fillers may be used alone or in combination of two or more. The content of these inorganic fillers is 0 to 95% by weight in the curable resin composition of the present invention.

  For the purpose of preventing coloring of the curable resin composition of the present invention, an amine compound as a light stabilizer or a phosphorus compound and a phenol compound as an antioxidant can be used. 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-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) 6-tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2,6,6, -tetramethyl 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] butyl Lonate, 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-2 , 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.

  A commercially available product can be used as the amine compound of the light stabilizer, and it is not particularly limited as a commercially available amine-based compound. TINUVIN 152, CHIMASSORB 944; manufactured by ADEKA, LA-52, LA-57, LA-62, LA-63P, LA-77Y, LA-81, LA-82, LA-87, and the like.

  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. .

  These phosphorus compounds can also be used as commercial products, and are not particularly limited as commercially available phosphorus compounds. For example, ADEKA's ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, Examples include ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 135A, ADK STAB 3010, and ADK STAB TPP.

  The phenolic 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-hydroxy. Phenyl) propionate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2,4-di-tert-butyl-6-methylphenol, 1,6-hexane Diol-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, pe Taerythrityl-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-butyl) Phenol), 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-pentylphenol, 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.

  A commercial item can also be used for said phenolic compound. It does not specifically limit as a phenolic compound marketed, For example, IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1135, IRGANOX245, IRGANOX259, manufactured by Ciba Specialty Chemicals; 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; Sumitizer GA-80 manufactured by Sumitomo Chemical Co., Ltd. , Sumilizer MDP-S, Sumilizer BB MS, Sumilizer GM, Sumilizer GS (F), Sumilizer GP, etc. are mentioned.

  In addition, a commercially available additive can be used as the anti-coloring agent for the resin, such as THINUVIN 328, THINUVIN 234, THINUVIN 326, THINUVIN 120, THINUVIN 477, THINUVIN 479, CHIMASSORB 2020FDL, and CHIMASSORB119FL manufactured by Ciba Specialty Chemicals.

  It is preferable to contain at least one of the above amine compounds, phosphorus compounds, and 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. , 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 can be 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.

  The content of the near-infrared absorbing dye used in the resin composition of the present invention is also appropriately determined according to the target near-infrared cut rate. 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, poly (vinylidene cyanide), vinylidene fluoride / trifluoroethylene copolymer, vinylidene fluoride / tetrafluoroethylene Copolymers, vinyl compounds such as vinylidene cyanide / vinyl acetate copolymers or copolymers of fluorine compounds, trees containing fluorine such as polytrifluoroethylene, polytetrafluoroethylene, polyhexafluoropropylene, etc. , Nylon 6, polyamide such as nylon 66, polyimide, polyurethane, polypeptide, polyester such as polyethylene terephthalate, polycarbonate, polyether polyoxymethylene or the like, epoxy resins, polyvinyl alcohol, polyvinyl butyral, and the like.

  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, 1) A near-infrared absorption pigment | dye is melt | dissolved in a thermosetting resin and a hardening | curing agent. The resin composition of the present invention, a method for producing a resin plate or film by heat-curing after molding, 2) A paint containing a near-infrared absorbing dye is produced, the resin composition of the present invention, and a transparent resin plate , A method for coating a transparent film, a transparent glass plate, or an image pickup device, 3) a composition containing a near-infrared absorbing dye and a resin (adhesive) is prepared, and the resin composition of the present invention is used as a laminated resin plate; A known method such as a method of producing a laminated resin film or a laminated glass plate can be used.

  In the method 1), a near-infrared absorbing dye is dissolved in a thermosetting resin and a curing agent, and as a resin composition of the present invention, injected into a mold or poured into a mold, and heated to react to obtain a cured product. The method of shaping | molding is mentioned. Depending on the composition used, the processing temperature, the conditions for film formation (resin plate formation) and the like differ somewhat, but curing conditions of about 30 minutes to 5 hours at 100 to 200 ° C. are usually 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 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. Although the density | concentration of a near-infrared absorption pigment | dye changes with thickness of the coating to produce, absorption intensity, and visible light transmittance | permeability, it is about 0.01-30 mass% normally with respect to 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.

  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, the insoluble dye may be mixed with other components while being dispersed into fine particles.

  As this method, a known method using a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer or the like can be mentioned, and among these, a sand mill (bead mill) is preferable. Further, in the pulverization of the pigment particles in the sand mill (bead mill), it is preferable to use a bead having a small diameter and to perform the treatment under the condition of increasing 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.

  When the near-infrared absorbing dye used in the near-infrared cut filter of the present invention is cationic, the counter anion is not particularly limited, but from the viewpoint of heat-resistant transparency of the cured product (optical filter), the following formula (15) A tris (perhalogenoalkylsulfonyl) imide anion represented by the following formula (16) or a tris (perhalogenoalkylsulfonyl) methide anion represented by the following formula (16) is preferred. 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 fluorine in the following formula (16).

（式中、ｘは１〜５、Ａはフッ素、塩素、臭素若しくはヨウ素を示す。）

（式中、ｘは１〜５、Ａはフッ素、塩素、臭素若しくはヨウ素を示す。）

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

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

  Although the specific example of the near-infrared absorption pigment | dye 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 light. When it is a cyanine compound, the compound No. 4 in Japanese Patent No. 4635007 (Patent Document 7) is used. 16 to 45, formulas (3) to (32) in Japanese Patent No. 3786408 (Patent Document 8), and compound No. 3 in JP-A-2007-1553836 (Patent Document 9). 1 to 16 and compound No. 1 in JP-A-2008-88426 (Patent Document 10). 16-57 are mentioned. In the case of a polymethine compound, compound No. 1 in JP-A No. 1983-219090 (Patent Document 11) is used. 1-20 are mentioned. In the case of a dimonium compound, No. 4 in Table 1 of Japanese Patent No. 4800769 (Patent Document 12). 1-150, No. 1 in Table 1 of WO2006 / 120888 (Patent Document 13). 1 to 20, Compound Nos. 1 to 3 in Tables 1 to 3 of JP-A No. 2003-96040 (Patent Document 14). 1-36, compound No. 1 in Table 1 of JP2007-197492A (Patent Document 15). 1-21 is mentioned. In the case of a phthalocyanine compound, the compounds described in the first group and the second group in JP-A No. 2000-026748 (Patent Document 6) can be mentioned. The compounds described in Table 1 are listed. When it is a metal dithiol complex, the following formula (17) is exemplified, and when it is a metal diamine complex, the following formula (18) is exemplified.

（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、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、置換又は未置換のアルキル基、あるいは置換又は未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。）

(In the formula, R _{10 to} R ₁₃ are the same or different from each other, hydrogen atom, halogen, cyano group, acyl group, carbamoyl group, alkylaminocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, substituted or unsubstituted alkyl 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、置換又は未置換のアルキル基、あるいは置換又は未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. 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. .)

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

  Examples of the acyl group include acetyl group, ethylcarbonyl group, propylcarbonyl group, butylcarbonyl group, pentylcarbonyl group, hexylcarbonyl group, benzoyl group, pt-butylbenzoyl group and the like.

  Examples of alkylaminocarbonyl group include methylaminocarbonyl group, ethylaminocarbonyl group, n-propylaminocarbonyl group, n-butylaminocarbonyl group, sec-butylaminocarbonyl group, n-pentylaminocarbonyl group, n-hexyl. Aminocarbonyl 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. That.

  Examples of the alkoxycarbonyl group include 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-dimethylpentoxyl Nyl group, 2-methyl-1-iso-propylpropyloxycarbonyl group, 1-ethyl-3-methylbutyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, 3-methyl-iso-propyl Linear or branched having 2 to 20 carbon atoms such as butyloxycarbonyl group, 2-methyl-1-iso-propyloxycarbonyl group, 1-t-butyl-2-methylpropyloxycarbonyl group, n-nonyloxycarbonyl group And alkyloxycarbonyl groups.

  Examples of the aryloxycarbonyl group include 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, examples of the unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, and a 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 Propyl group, n- nonyl, 3,5,5 linear 1 to 20 carbon atoms such as trimethyl hexyl group, and a hydrocarbon group branched or cyclic.

  The substituted alkyl group is a group in which at least one hydrogen of the above-described unsubstituted alkyl group is substituted with various functional groups. For example, an alkoxyalkyl group in which the hydrogen of an unsubstituted alkyl group is substituted with an alkoxy group, an alkoxyalkoxyalkyl group in which the hydrogen of an unsubstituted alkyl group is substituted with an alkoxyalkoxy group, or the hydrogen of an unsubstituted alkyl group is an alkoxyalkoxy group An alkoxyalkoxyalkyl group substituted with an alkoxy group, a halogenated alkyl group in which the hydrogen of the unsubstituted alkyl group is substituted with a halogen atom, an aminoalkyl group in which the hydrogen of the unsubstituted alkyl group is substituted with an amino group, Examples thereof include alkylaminoalkyl groups and dialkylaminoalkyl groups in which hydrogen of the substituted alkyl group is substituted with alkylamino groups, other alkoxycarbonylalkyl groups, alkylaminocarbonylalkyl groups, alkoxysulfonylalkyl groups, and the like.

  Alkoxyalkyl groups include methoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, methoxyethoxymethyl, ethoxyethoxyethyl, dimethoxymethyl Group, diethoxymethyl group, dimethoxyethyl group, diethoxyethyl group and the like. Examples of the halogenated alkyl group include chloromethyl group, 2,2,2-trichloroethyl group, trifluoromethyl group, 1,1. 1,3,3,3-hexafluoro-2-propyl group and the like.

  Among the substituted or unsubstituted aryl groups, examples of the unsubstituted one include a phenyl group, a naphthyl group, a biphenyl group, and the like. The substituted aryl group includes various kinds of at least one hydrogen of the above-described unsubstituted aryl group. The functional group is substituted. For example, the substituted phenyl group includes a halogenated phenyl group such as a chlorophenyl group, a dichlorophenyl group, a trichlorophenyl group, a bromophenyl group, a fluorophenyl group, a pentafluorophenyl group, and a phenyl iodide group, a tolyl group, a xylyl group, and a mesityl group. Alkylphenyl-substituted phenyl groups such as ethylphenyl group, dimethylethylphenyl group, iso-propylphenyl group, t-butylphenyl group, t-butylmethylphenyl group, octylphenyl group, nonylphenyl group, trifluoromethylphenyl group, Methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group, isopropoxyphenyl group, hexyloxyphenyl group, cyclohexyloxyphenyl 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, ethoxyethoxyethoxyphenyl 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) siphenyl group, 3-iso-propoxy-4- Alkoxy substitution such as (2-ethoxyethoxy) siphenyl group, 2- (2-hydroxy) -3-methoxyphenyl group, 3-methoxy-4- (2-hydroxyethoxy) phenyl group, chloromethoxyphenyl group, chloroethoxyphenyl group Phenyl group, methylthiophenyl group, ethylthiophenyl group, t-butylthiophenyl group Alkylthio group-substituted phenyl groups such as di-tert-butylthiophenyl group and 2-methyl-1-methylthiophenyl group, N, N-dimethylaminophenyl group, N, N-diethylaminophenyl group, N, N-dipropyl Aminophenyl group, N, N-dibutylaminophenyl group, N, N-diamylaminophenyl group, N, N-dihexylaminophenyl group, N-methyl-N-ethylaminophenyl group, N-butyl-N-ethyl Aminophenyl group, N-hexyl-N-ethylaminophenyl group, 4- (N, N-dimethylamino) -ethylphenyl group, 4- (N, N-diethylamino) -ethylphenyl group, 3- (N, N -Dimethylamino) -ethylphenyl group, alkylaminophenyl group such as 2- (N, N-dimethylamino) -ethylphenyl group, etc. And the like.

  Examples of the substituted naphthyl group include a chloronaphthyl group, a dichloronaphthyl group, a trichloronaphthyl group, a bromonaphthyl group, a fluoronaphthyl group, a pentafluoronaphthyl group, a iodide naphthyl group, and the like, an ethylnaphthyl group, and dimethylethyl Naphthyl group, iso-propyl naphthyl group, t-butyl naphthyl group, t-butylmethyl naphthyl group, octyl naphthyl group, nonyl naphthyl group, trifluoromethyl naphthyl group alkyl derivative substituted 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 group such as methoxynaphthyl 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, N, N-diethylaminonaphthyl group, N, N-dipropylaminonaphthyl group, N, N-dibutylaminonaphthyl group, N, N-dia, such as methylthionaphthyl group 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) -ethylnaphthy Alkylaminonaphthyl such as 4-, (N, N-diethylamino) -ethylnaphthyl group, 3- (N, N-dimethylamino) -ethylnaphthyl group, 2- (N, N-dimethylamino) -ethylnaphthyl group Groups.

  In addition to these, the substituted or unsubstituted aryl group includes a substituted or unsubstituted p-nitrophenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrrolidyl group, a substituted or unsubstituted piperidyl group, a 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 can also be mentioned.

  Particularly preferred substituents represented by R10 to R17 of the thiol metal complex compounds represented by the above formulas (15) and (16) are the same or different alkyl groups, phenyl groups, naphthyl groups, and tolyl groups. , 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-dibutylaminophenyl group, ethylnaphthyl group, dimethylethylnaphthyl group, iso-propylnaphthyl group, t-butylnaphthyl group, t-butylmethylnaphthyl group, Methoxynaphthyl group, ethoxynaphthyl group, propoxynaphthyl Group, methylthionaphthyl group, ethylthionaphthyl group, t-butylthionaphthyl group, methylethylthionaphthyl group, butylmethylthionaphthyl group, N, N-dimethylaminonaphthyl group, N, N-diethylaminonaphthyl group, N, N A substituted or unsubstituted alkyl group having 3 to 20 carbon atoms, such as a dipropylaminonaphthyl group or N, N-dibutylaminonaphthyl group, 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 dispersed or mixed by the above method.

  The optical filter of the present invention for absorbing near infrared rays is used not only for imaging device applications and display front plates, but also for filter films that need to cut near infrared rays, such as heat insulating films, optical products, sunglasses, etc. I can do it.

Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples. The present invention is not limited to these synthesis examples and examples. In addition, each physical-property value in a synthesis example and an Example was measured with the following method. Here, the part represents part by weight unless otherwise specified.
○ Weight average molecular weight: It was calculated by polystyrene conversion measured under the following conditions by the GPC method.
GPC measurement conditions Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)
○ Spectral characteristics: UV-visible spectrophotometer UV-3150 (manufactured by Shimadzu Corporation)
○ Acid value: measured by the method described in JIS K-2501.
○ Epoxy equivalent: Measured by the method described in JIS K-7236.
○ Viscosity: Measured using an E-type viscometer at 25 ° C.

[Synthesis Example 1] (Synthesis of a condensation product of a silicon compound having an epoxy group and another silicon compound)
394 parts of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 475 parts of polydimethyldiphenylsiloxane having a silanol group with a molecular weight of 1700 (measured by GPC), 4 parts of 0.5% KOH methanol solution, 36 parts of isopropyl alcohol Was charged into a reaction vessel and heated to 75 ° C. After raising the temperature, the reaction was carried out under reflux for 10 hours. Then, it cooled to room temperature and added 656 parts of methanol. Thereafter, 172.8 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes, the temperature was raised to the reflux temperature, and the reaction was further continued for 10 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, neutralized with 5% aqueous sodium hydrogen phosphate solution, heated to 80 ° C., and methanol was recovered by distillation. Thereafter, the mixture was cooled to room temperature, 780 parts of methyl isobutyl ketone (MIBK) was added for washing, and washing with water was repeated three times. Next, the organic phase was removed under reduced pressure at 100 ° C. to obtain 731 parts of a silicone skeleton epoxy resin (X). The obtained compound (X) had an epoxy equivalent of 491 g / eq, a weight average molecular weight of 2090, a viscosity of 3328 mPa · s, and the appearance was colorless and transparent.

[Synthesis Example 2] (Synthesis of a condensate between a silicon compound having an epoxy group and another silicon compound)
111 parts of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 100 parts of polydimethyldiphenylsiloxane having a silanol group with a molecular weight of 1700 (measured by GPC), 1 part of 0.5% KOH methanol solution, 8 parts of isopropyl alcohol Was charged into a reaction vessel and heated to 75 ° C. After raising the temperature, the reaction was carried out under reflux for 10 hours. Then, 120 parts of methanol was added, 48.6 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was further reacted for 10 hours under reflux. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium hydrogen phosphate solution, heated to 80 ° C., and methanol was recovered by distillation. Thereafter, the mixture was cooled to room temperature, 174 parts of MIBK was added for washing, and washing with water was repeated three times. Next, the organic phase was removed under reduced pressure at 100 ° C. to obtain 174 parts of a silicone skeleton epoxy resin (Y). The compound (Y) obtained had an epoxy equivalent of 411 g / eq, a weight average molecular weight of 3200, a viscosity of 15140 mPa · s, and the appearance was colorless and transparent.

[Synthesis Example 3] (Synthesis Example of Polycarboxylic Acid Resin)
In a glass separable flask equipped with a stirrer, a Dimroth condenser, and a thermometer, 243.5 parts X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.), a terminal carbinol-modified silicone, and ADEKA NEW ACE, a polyester polyol Y9-10 (made by ADEKA Corporation, polyester polyol in which R ₆ is a neopentyl group and R ₇ is a butyl group in the above formula (3)) 60.9 parts, containing one carboxylic anhydride group in the molecule Ricacid MH (methyl hexahydrophthalic anhydride, manufactured by Shin Nippon Rika Co., Ltd.) 83.5 parts, Ricacid BT-100 (compound containing two or more carboxylic anhydride groups in the molecule) 12.3 parts of butanetetracarboxylic dianhydride (manufactured by Shin Nippon Rika) By the time the reaction to give the polycarboxylic acid resin (Z) 400 parts. At this time, the peaks of Ricacid BT-100 and Ricacid MH disappeared in the GPC measurement. The obtained compound (Z) was an acid value of 76.7 mgKOH / g, a weight average molecular weight of 3452, a viscosity of 5730 mPa · s, and the appearance was a colorless and transparent liquid.

[Example 1]
In a glass separable flask equipped with a stirrer and a thermometer, 72.4 parts of the polyvalent carboxylic acid resin (Z) obtained in Synthesis Example 3 as an epoxy resin curing agent, and 0.55 zinc stearate as a curing accelerator. The zinc stearate was dissolved in the polyvalent carboxylic acid resin (Z) while stirring at 60 ° C. for 1 hour. Thereafter, it was allowed to cool to 28 ° C., and 40 parts of the silicone skeleton epoxy resin (X) obtained in Synthesis Example 1 as an epoxy resin, 60 parts of the silicone skeleton epoxy resin (Y) obtained in Synthesis Example 2, ERL-4221 ( 5.0 parts of 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate, manufactured by Dow Chemical) was added and stirred at 28 ° C. until uniform. 150 parts of chloroform and 1.0 part of the following formula (13) (Compound 31 described in JP-A-2008-88426, λmax in chloroform: 831 nm) are added thereto and stirred at 28 ° C. until uniform. Thus, the 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. This optical filter was allowed to stand at 210 ° C. for 10 minutes, and the heat resistance was evaluated by comparing spectral waveforms before and after heating.

[Comparative Example 1]
In a glass separable flask equipped with a stirrer and a thermometer, 700 parts of chloroform, 300 parts of diallyl phthalate resin (manufactured by Daiso Co., Ltd., trade name “Daisodap S”), the same infrared absorbing dye 0.80 as in Example 1 And the mixture was sufficiently stirred at 28 ° C. to obtain a comparative resin composition. This resin composition is dropped on 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. An optical filter was obtained. This optical filter was allowed to stand at 150 ° C. for 3 hours and then at 210 ° C. for 10 minutes, and the heat resistance was evaluated by comparing spectral waveforms before and after heating.

[optical properties]
Using the spectrophotometer, the absorbance of each optical filter of Example 1 and Comparative Example 1 was measured in the range of 300 to 1100 nm at a sampling pitch of 1 nm. Table 1 shows changes in absorbance at the maximum absorption wavelength (830 nm) before and after the heat resistance test of the optical filters of Example 1 and Comparative Example 1.

Table 1

  Normalization was performed so that the initial absorbance A1 in Table 1 was used as a reference, and Table 2 was obtained.

Table 2

  It can be said that as the values of B2 and B3 are larger, the near-infrared light absorption decay with respect to the heat load is smaller, and the near-infrared cut filter is excellent in heat resistance. From the results shown in Table 2, B2 and B3 in Comparative Example 1 both showed lower values than B2 and B3 in Example 1, indicating inferior results as near-infrared cut filters.

  The thermosetting resin composition of the present invention and the near-infrared cut filter (optical filter) obtained thereby are spin coatable as a resin solution, in addition to having a small deterioration of near-infrared absorption and high weather resistance even when a thermal load is applied. Therefore, it 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. .

Claims (12)

A resin composition containing an epoxy resin (A), an epoxy resin curing agent (B), and a near-infrared absorbing dye (C). The resin composition according to claim 1, wherein the epoxy resin (A) is a silicone skeleton epoxy resin. The curable resin composition according to claim 1 or 2, wherein the silicone skeleton epoxy resin is synthesized through the following two-step reaction.
First stage reaction: a condensation reaction between the silanol-terminated silicone oil (a) represented by the general formula (1) and the epoxy group-containing silicon compound (b) represented by the general formula (2).
Second stage reaction: dealcoholization hydrolysis condensation reaction of alkoxy group by reaction between the reaction product obtained in the first stage reaction and added water.

(In the formula, R ₁ may be the same or different from each other, and is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or 2 carbon atoms. 10 represents an alkenyl group, and m represents an average value of 2 to 2000.)

(In the formula, X is a substituent having an epoxy group, R ₂ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aryl group having an aromatic hydrocarbon group having 6 to 10 carbon atoms. R ₃ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, p represents an integer of 0, 1, 2 and q represents (3-p).) The curable resin composition according to any one of claims 1 to 3, wherein the epoxy resin curing agent (B) is a polyvalent carboxylic acid resin. The curable resin composition (c) according to claim 4, wherein the polyvalent carboxylic acid resin is an addition polymer of a compound containing the following (c) and (d): containing two or more hydroxyl groups in the molecule A polyhydric alcohol compound.
(D); a compound containing one or more acid anhydride groups in the molecule. The curable resin composition (c) according to claim 4, wherein the polyvalent carboxylic acid resin is an addition polymer of a compound containing the following (c) to (e): containing two or more hydroxyl groups in the molecule Polyhydric alcohol compound.
(D); a compound containing one or more acid anhydride groups in the molecule.
(E): Both ends carbinol-modified silicone oil. The curable resin composition according to claim 6, characterized by the following (l) to (n).
(L): The polyhydric alcohol compound (c) containing two or more hydroxyl groups in the molecule has the structure of the following formula (3).
(M): The compound (d) containing one or more acid anhydride groups in the molecule is at least one selected from the group consisting of the following formulas (4) to (11).
(N): Both end carbinol-modified silicone oil (e) has the structure of the following formula (12).

(Wherein R ₆ and R ₇ each independently represents an alkylene group having 1 to 10 carbon atoms, and m represents an average value of 1 to 1000).

(In the formula, each R ₄ is independently an alkylene group having 1 to 10 carbon atoms or an alkylene group containing an ether bond having 1 to 10 carbon atoms, R ₅ is each independently a methyl group or a phenyl group, and n is an average value. Represents 1 to 1000.) The near-infrared absorbing dye (C) contains at least one kind selected from a cyanine compound, a polymethine compound, a diimonium compound, a phthalocyanine compound, a naphthalocyanine compound, a metal dithiol complex, and a metal diamine complex. Item 8. The resin composition according to any one of Items 1 to 7. The resin composition according to any one of claims 1 to 7, wherein the near-infrared absorbing dye (C) is at least one cyanine compound. The resin composition according to any one of claims 1 to 7, wherein the methine chain of the cyanine compound according to claim 9 has 5 or more carbon atoms. The near-infrared cut filter using the resin composition as described in any one of Claims 1 thru | or 10. An image sensor comprising the near infrared cut filter according to claim 11.