JP2014026070A - Near-infrared-ray-absorbing composition, near-infrared-ray cut filter using the same and production method thereof, and camera module and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a near-infrared-ray-absorbing composition containing a phosphate ester copper complex having a wavelength of greatest absorption that has been shifted to a longer wavelength side.SOLUTION: The near-infrared-ray-absorbing composition contains a phosphate ester copper complex that can be obtained by reacting greater than 2 moles of a phosphate ester compound with one mole of a copper salt.

Description

  The present invention relates to a near-infrared absorbing composition, a near-infrared cut filter using the same, a manufacturing method thereof, a camera module, and a manufacturing method thereof.

  In recent years, CCDs and CMOS image sensors, which are solid-state image sensors for color images, have been used in video cameras, digital still cameras, mobile phones with camera functions, etc., but these solid-state image sensors are sensitive to near infrared rays in their light receiving parts. Therefore, it is necessary to correct visibility, and a near-infrared cut filter is often used.

  As a material for forming such a near-infrared cut filter, a near-infrared absorbing composition is known (Patent Document 1, Patent Document 2).

Japanese Patent Laid-Open No. 11-52127 JP 2000-38396 A

When the inventor examined the above Patent Document 1 and Patent Document 2, when a near-infrared cut filter was produced using the copper phosphate ester complexes described therein, the wavelength shifted to the short wavelength side with the maximum absorption wavelength. It turns out that there is a case. Furthermore, when this inventor examined, when the near-infrared absorptive composition was made into a layer form by application | coating and this near-infrared cut filter was produced, it turned out that this tendency is remarkable.
An object of the present invention is to provide a near-infrared absorptive composition comprising a phosphate ester copper complex in which the maximum absorption wavelength is shifted to the longer wavelength side. To do.

Under such circumstances, as a result of intensive studies by the present inventor, in forming a phosphate copper complex, phosphorus obtained by reacting more than 2 mol of a phosphate ester compound with respect to 1 mol of a copper salt. It has been found that the maximum absorption wavelength can be shifted to the long wavelength side by using an acid ester copper complex. Although this mechanism is not clear, the addition of more than 2 moles of phosphate ester compound to 1 mole of copper salt results in a highly coordinated complex because the phosphate group is coordinated to the axial position of copper. It is considered that the waveform shifts to the long wavelength side.
Specifically, the above problem has been solved by the following means <1>, preferably by <2> to <11>.
The near-infrared absorptive composition containing the phosphate ester copper complex obtained by making more than 2 mol react the phosphoric ester compound with respect to 1 mol of <1> copper salt.
<2> The maximum absorption wavelength is shifted to the longer wavelength side than the phosphate ester copper complex obtained by reacting 2 mol of the phosphate ester compound with respect to 1 mol of copper. The near-infrared absorptive composition as described in <1>.
<3> The near-infrared absorbing composition according to either <1> or <2>, further comprising a compound having a polymerizable group and a solvent.
<4> The near-infrared absorbing composition according to any one of <1> to <3>, wherein the phosphate ester compound is formed using a compound represented by the following formula (1).
Formula (1)
_{(HO) n -P (= O} ) - (OR 2 Q) 3-n
(In the formula, Q represents a hydrogen atom or a polymerizable group, R ² represents a divalent linking group, and n represents 1 or 2.)
<5> The near-infrared absorbing composition according to <4>, wherein the phosphate ester compound is a mixture of a compound in which n is 1 and a compound in which n is 2 in formula (1).
<6> The near-infrared absorbing composition according to any one of <1> to <5>, wherein a maximum absorption wavelength of the phosphate ester copper complex is 800 nm or more.
<7> Near-infrared cut filter produced using the near-infrared absorptive composition in any one of <1>-<6>.
<8> Production of a near-infrared cut filter having a step of forming a film by applying the near-infrared absorbing composition according to any one of <1> to <6> on the light receiving side of the solid-state imaging device substrate. Method.
<9> Obtained by the method for manufacturing a solid-state image sensor substrate and the near-infrared cut filter according to <7>, or the near-infrared cut filter according to <8>, disposed on the light-receiving side of the solid-state image sensor substrate. And a near-infrared cut filter.
<10> A method of manufacturing a camera module having a solid-state image sensor substrate and a near-infrared cut filter arranged on the light-receiving side of the solid-state image sensor substrate, wherein <1> to The manufacturing method of a camera module which has the process of forming a film | membrane by apply | coating the near-infrared absorptive composition of any one of <6>.
<11> The method for producing a camera module according to <10>, comprising curing the film formed by applying the near-infrared absorbing composition by light irradiation.
<12> A phosphate ester copper complex obtained by reacting more than 2 mol of a phosphate ester compound with respect to 1 mol of a copper salt.
<13> A method for producing a phosphate ester copper complex, comprising reacting more than 2 mol of a phosphate ester compound with respect to 1 mol of a copper salt.

Further, the above-mentioned problem has been solved by the following means.
<14> The near-infrared absorbing composition according to any one of the above, wherein the compound having a polymerizable group is a polyfunctional monomer.
<15> The near-infrared absorbing composition according to any one of the above, wherein the compound having a polymerizable group is a polymerizable monomer represented by the following general formulas (MO-1) to (MO-6). The near-infrared absorptive composition characterized by the above-mentioned.
(In the formula, each of n is 0 to 14 and m is 1 to 8. Each of R, T and Z present in a molecule is the same or different. When T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R. At least one of R is a polymerizable group.)
<16> The near-infrared absorbing composition according to any one of the above, wherein the compound having a polymerizable group is a polymer having a polymerizable group in a side chain.
<17> The near-infrared absorbing composition according to any one of the above, further comprising a polymerization initiator.
<18> The near-infrared absorbing composition according to any one of the above, wherein the compound having a polymerizable group contains a (meth) acryloyloxy group.
<19> The near-infrared absorptive composition according to any one of the above, wherein the near-infrared absorptivity is obtained by reacting a phosphoric acid ester compound of more than 2 moles and 10 moles or less with respect to 1 mole of copper salt Composition.
<20> The near-infrared absorbing composition according to any one of the above, wherein the phosphate ester copper complex is obtained by reacting 2 mol of a phosphate ester compound with respect to 1 mol of copper. The near-infrared absorptive composition in which the maximum absorption wavelength is shifted to the longer wavelength side by 20 nm or more than the complex.

  According to the present invention, it is possible to provide a near-infrared absorptive composition containing a phosphate ester copper complex whose maximum absorption wavelength is shifted to the long wavelength side. Such a composition can be particularly preferably used when a near-infrared filter is formed by coating.

It is a schematic sectional drawing which shows the structure of the camera module provided with the solid-state image sensor which concerns on embodiment of this invention. It is a schematic sectional drawing of the solid-state image sensor board | substrate which concerns on embodiment of this invention. It is a figure which shows the light absorbency in each wavelength of the solution prepared in the Example of this application. It is a figure which shows the light absorbency in each wavelength of the solid prepared in the Example of this application.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl. In the present specification, “monomer” and “monomer” are synonymous. The monomer in the present invention is distinguished from an oligomer and a polymer and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction. In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The near infrared ray in the present invention refers to those having a wavelength region of 700 to 2500 nm.

  The near-infrared absorptive composition of the present invention, a near-infrared cut filter, a camera module having such a near-infrared cut filter and a solid-state imaging device substrate, and a method for producing the camera module will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

  The near-infrared absorbing composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) is a phosphoric acid obtained by reacting more than 2 mol of a phosphate ester compound with respect to 1 mol of a copper salt. It contains an ester copper complex. Hereinafter, these contents will be described in detail.

<Phosphate ester copper complex>
The phosphate ester copper complex contained in the composition of the present invention is obtained by reacting more than 2 mol of the phosphate ester compound with respect to 1 mol of the copper salt. The amount of the phosphate ester compound to be reacted is preferably more than 2 mol and 20 mol or less, more preferably more than 2 mol and 15 mol or less, relative to 1 mol of copper salt, More preferably, it is mol, and 4-6 mol is especially preferable. In this way, by reacting an excessive phosphate ester compound with a copper salt, the maximum absorption wavelength is higher than the phosphate ester copper complex obtained by reacting 2 mol of the phosphate ester compound with respect to 1 mol of copper. It becomes possible to shift to the long wavelength side. Specifically, the phosphate copper complex used in the present invention can shift the maximum absorption wavelength to the longer wavelength side, and can further shift it by 10 nm or more, and more preferably 20 nm or more. It is possible to shift. There is no particular upper limit on the wavelength to be shifted, but it is practical that the shift is 30 nm or less.
Since it can be shifted to the long wavelength side in this way, the maximum absorption wavelength can be 790 nm or more, further 800 nm or more, and particularly 810 nm or more. The copper phosphate ester complex used in the present invention preferably has a maximum absorption wavelength at 790 to 850 nm, more preferably 800 to 850 nm, and particularly preferably 810 to 850 nm.
The composition of the present invention preferably contains the phosphate ester copper complex in a proportion of 20 to 95% by mass, more preferably 30 to 80% by mass, based on the total solid content excluding the solvent. It is particularly preferable to include 60 to 80% by mass. In particular, the phosphate ester copper complex obtained by reacting 70% by mass or more of the phosphate ester copper complex contained in the composition of the present invention with more than 2 mol of the phosphate ester compound with respect to 1 mol of the copper salt. It is preferable that it is 80% by mass or more, more preferably 90% by mass or more.

<Method for producing phosphate copper complex>
The phosphate ester copper complex used in the present invention is not particularly defined as long as it is obtained by reacting more than 2 mol of the phosphate ester compound with respect to 1 mol of the copper salt, and adopts a known method. Can be manufactured. For example, the description of International Publication WO99 / 26952 can be taken into account, and the contents of this specification are incorporated in the present specification.
Preferably, the phosphate ester copper complex is prepared by dissolving a phosphate ester compound in an amount of more than 2 moles in 1 mol of a copper salt in a solvent that dissolves both of them, for example, acetone, and at room temperature for a desired time. For example, the reaction is allowed to proceed for 3 hours.
The copper salt used here is preferably divalent or trivalent copper, and more preferably divalent copper.
Copper salts include copper acetate, copper chloride, copper formate, copper stearate, copper benzoate, copper ethyl acetoacetate, copper pyrophosphate, copper naphthenate, copper citrate, copper nitrate, copper sulfate, copper carbonate, copper chlorate Copper (meth) acrylate is more preferable, copper benzoate and copper (meth) acrylate are more preferable. These may be anhydrous or hydrated.

  The obtained phosphoric acid ester copper complex may be used as it is, but preferably, it may be purified by washing with a solvent to extract and remove the acid component as a by-product. This purification prevents degradation of spectral characteristics at high temperatures and further prevents decomposition reactions. Solvents used for extraction and removal of this acid component include water, aliphatic lower alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and ethyl ether. Ethers such as ethyl acetate, esters such as ethyl butyl acetate, petroleum ether, n-pentane, n-hexane, n-heptane, chloroform, methylene chloride, aliphatic hydrocarbons such as carbon tetrachloride and their halides, Aromatic compounds such as benzene, toluene and xylene are used. These solvents are used alone or in combination.

The phosphate ester compound used in the present invention is more preferably formed using a compound represented by the following formula (1), which can widely employ known compounds.
Formula (1)
_{(HO) n -P (= O} ) - (OR 2 Q) 3-n
(In the formula, Q represents a hydrogen atom or a polymerizable group, R ² represents a divalent linking group, and n represents 1 or 2.)

Q represents a hydrogen atom or a polymerizable group. Examples of the polymerizable group include an unsaturated polymerizable group, an epoxy group, and an aziridinyl group. Of these, unsaturated polymerizable groups are preferred. Examples of the unsaturated polymerizable group include an ethylenically unsaturated polymerizable group, and among the ethylenically unsaturated polymerizable groups, an acryloyl group, a methacryloyl group, and the like are preferable.
Q is preferably a polymerizable group from the viewpoint of ease of improving the concentration of the composition of the present invention when forming a film by applying the composition of the present invention, film strength, and film physical properties. .
R ² represents a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 18 carbon atoms, an arylene group having 6 to 18 carbon atoms, an aralkylene group having 7 to 18 carbon atoms, or an alkenylene group having 2 to 18 carbon atoms, and 1 And a group consisting of a combination of one or more and one or more -O-. The divalent linking group is preferably an alkylene group having 1 to 18 carbon atoms or a group composed of a combination of one or more alkylene groups having 1 to 18 carbon atoms and one or more —O—.
The alkylene group having 1 to 18 carbon atoms is preferably a linear or branched alkylene group. The alkylene group preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 7 carbon atoms.
The arylene group having 6 to 18 carbon atoms preferably has 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, and still more preferably 6 carbon atoms.
The aralkylene group having 7 to 18 carbon atoms preferably has 7 to 10 carbon atoms, more preferably 7 to 9 carbon atoms, and still more preferably 7 to 8 carbon atoms.
The alkenylene group having 2 to 18 carbon atoms preferably has 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms, and still more preferably 2 to 8 carbon atoms.

The divalent linking group represented by R ² may have a substituent, for example, a halogen atom, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group , Hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonyl Amino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or aryl Sulfini Group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group And a silyl group.

Particularly in the present invention, among the compounds represented by the formula (1), R ² is a linear or branched alkylene group having 1 to 18 carbon atoms, an arylene group having 6 to 18 carbon atoms, and A group consisting of a combination of one or more of these and one or more -O- is preferred. These may have the aforementioned substituents. Further, when Q is a polymerizable group, R ² is preferably a linear or branched alkylene group having 1 to 18 carbon atoms and a group comprising a combination of this alkylene group and one or more —O—. These may have the aforementioned substituents.

When n is 1, two —OR ² Q may be the same or different.
In the present invention, it is preferable that n is a mixture of the compound of 1 and the compound of 2.

The phosphate ester compound used in the present invention may be a monoester or a diester, but is preferably a mixture of a monoester and a diester. By blending the phosphoric acid diester compound, the solubility of the phosphoric acid ester compound mixture can be improved, and by blending the phosphoric acid monoester, the maximum absorption wavelength of the resulting phosphoric acid ester copper compound is longer wavelength side. It becomes easy to shift to. The mixing ratio (mass ratio) of the phosphoric acid monoester compound and the phosphoric acid diester compound is preferably 5: 1: to 1: 5, and more preferably 3: 1 to 1: 3.
The molecular weight of the phosphate ester compound used in the present invention is preferably 300-1500, and more preferably 320-900.

  Below, the phosphate ester compound used as the raw material of the phosphate ester copper complex preferably used by this invention is shown. Needless to say, the present invention is not limited to these examples.

  Of the phosphoric acid ester compounds PE-1 to PE-61 used for forming the phosphoric acid ester copper complex, PE-15 to PE-61 are preferable, and PE-47, PE-48, and PE-49 are more preferable. PE-58, PE-59, PE-60, and PE-61, and particularly preferred are PE-47, PE-48, PE-58, PE-59, PE-60, and PE-61.

Below, the preferable combination of the phosphate ester compound and copper salt of this invention is shown. Needless to say, the present invention is not limited to these examples.
(1) In the phosphoric acid ester compound represented by formula (1), R ² is one or more alkylene groups having 1 to 18 carbon atoms (preferably an alkylene group having 1 to 5 carbon atoms) and one or more —O—. The aspect which is group which consists of a combination of these.
(2) In the above (1), the copper salt is copper acetate, copper chloride, copper formate, copper stearate, copper benzoate, copper ethyl acetoacetate, copper pyrophosphate, copper naphthenate, copper citrate, copper nitrate, copper sulfate , Copper carbonate, copper chlorate, copper acrylate, and anhydrides or hydrates thereof.
(3) In the above (1), the copper salt is copper acetate, copper benzoate, copper nitrate, copper sulfate, copper carbonate, copper chlorate, copper chloride, copper (meth) acrylate, and anhydrides or water thereof. An embodiment selected from Japanese.
(4) In the above (1), the copper salt is selected from copper acetate, copper benzoate and copper (meth) acrylate.
(5) above in any of the embodiments, aspects -OR ² Q in the formula (1) contains an ester group.
(6) In any one of the above embodiments, Q in Formula (1) is a polymerizable group.
(7) In any one of the above embodiments, Q in formula (1) is a (meth) acryloyl group.
(8) In any one of the above embodiments, the phosphate ester compound is a mixture of n and 1 in formula (1).

<Compound having a polymerizable group>
The composition of the present invention preferably contains a compound having a polymerizable group (hereinafter sometimes referred to as “polymerizable compound”). Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be any of chemical forms such as a monomer, an oligomer, a prepolymer, and a polymer.
The polymerizable compound may be monofunctional or polyfunctional, but is preferably polyfunctional. By including a polyfunctional compound, the near-infrared shielding property and heat resistance can be further improved. The number of functional groups is not particularly defined, but 2 to 8 functional groups are preferable.

<< A: Polymerizable monomer and polymerizable oligomer >>
In a first preferred embodiment of the composition of the present invention, a polymerizable compound is a monomer having a polymerizable group (polymerizable monomer) or an oligomer having a polymerizable group (polymerizable oligomer) (hereinafter, polymerizable with a polymerizable monomer). In some embodiments, the polymerizable oligomers may be collectively referred to as “polymerizable monomers”.

Examples of the polymerizable monomer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides. These are esters of saturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid.
As these specific compounds, the compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.

The polymerizable monomer or the like is also preferably a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as annulate, glycerin and trimethylolethane; Urethane (meth) acrylates as described in JP-B-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy polymers and (meth) acrylic acid, and mixtures thereof.
A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
Further, as other preferable polymerizable monomers, etc., compounds having a fluorene ring and having two or more functional ethylenic polymerizable groups described in JP 2010-160418 A, JP 2010-129825 A, Patent 4364216, etc. Polymers can also be used.

  Further, compounds having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group are disclosed in paragraphs [0254] to [0257] of JP-A-2008-292970. The compounds described are also suitable.

  In addition, a compound which has been (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. Can be used as a polymerizable monomer.

The polymerizable monomer used in the present invention is further preferably a polymerizable monomer represented by the following general formulas (MO-1) to (MO-6).
(In the formula, each of n is 0 to 14 and m is 1 to 8. Each of R, T and Z present in a molecule is the same or different. When T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R. At least one of R is a polymerizable group.)

n is preferably 0 to 5, and more preferably 1 to 3.
m is preferably 1 to 5, and more preferably 1 to 3.
R is
Is preferred,
Is more preferable.
Specific examples of the radical polymerizable monomer represented by the above general formulas (MO-1) to (MO-6) include compounds described in paragraph numbers 0248 to 0251 of JP-A No. 2007-26979. Can also be suitably used in the present invention.

Among them, as a polymerizable monomer, dipentaerythritol triacrylate (KAYARAD D-330 as a commercially available product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D-320; Nippon Kayaku) Dipentaerythritol penta (meth) acrylate (manufactured by K.K.) and dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; Nippon Kayaku Co., Ltd.) Company), and these (meth) acryloyl groups via ethylene glycol and propylene glycol residues, diglycerin EO (ethylene oxide) modified (meth) acrylate (M-460 as a commercial product; ) Preferred. These oligomer types can also be used.
For example, RP-1040 (made by Nippon Kayaku Co., Ltd.) etc. are mentioned.

  As a polymerizable monomer etc., it is a polyfunctional monomer, Comprising: You may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. The acid group may be introduced by reacting the group with a non-aromatic carboxylic acid anhydride. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronics series M-305, M-510, and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. When two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, it is essential that the acid value of the entire polyfunctional monomer is within the above range. It is.

Moreover, it is preferable to contain the polyfunctional monomer which has a caprolactone modified structure as a polymerizable monomer.
The polyfunctional monomer having a caprolactone-modified structure is not particularly limited as long as it has a caprolactone-modified structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane , Which is obtained by esterifying a polyhydric alcohol such as pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone, Mention may be made of functional (meth) acrylates. Among these, a polyfunctional monomer having a caprolactone-modified structure represented by the following formula (1) is preferable.

(In the formula, all 6 Rs are groups represented by the following formula (2), or 1 to 5 of 6 Rs are groups represented by the following formula (2), The remainder is a group represented by the following formula (3).)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.)

The polyfunctional monomer having such a caprolactone-modified structure is commercially available, for example, as KAYARAD DPCA series from Nippon Kayaku Co., Ltd., and DPCA-20 (m = in the above formulas (1) to (3)) 1, the number of groups represented by formula (2) = 2, a compound in which R ¹ is all hydrogen atoms, DPCA-30 (same formula, m = 1, number of groups represented by formula (2) = 3, compound in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (2) = 6, compound in which R ¹ is all hydrogen atoms), DPCA -120 (a compound in which m = 2 in the formula, the number of groups represented by formula (2) = 6, and all R ¹ are hydrogen atoms).
In this invention, the polyfunctional monomer which has a caprolactone modified structure can be used individually or in mixture of 2 or more types.

  In addition, the polymerizable monomer or the like in the present invention is preferably at least one selected from the group of compounds represented by the following general formula (i) or (ii).

In the general formula (i) and (ii), E are each _{independently, - ((CH 2) yCH} 2 O) -, or _{- ((CH 2) y CH} (CH 3) O) - represents, Each y independently represents an integer of 0 to 10, and each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
In said general formula (i), the sum total of acryloyl group and methacryloyl group is 3 or 4, m represents the integer of 0-10 each independently, and the sum of each m is an integer of 0-40. However, when the total of each m is 0, any one of X is a carboxyl group.
In said general formula (ii), the sum total of acryloyl group and methacryloyl group is 5 or 6, n represents the integer of 0-10 each independently, and the sum total of each n is an integer of 0-60. However, when the total of each n is 0, any one of X is a carboxyl group.

In the general formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable as the sum total of each m.
In the general formula (ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In general formula (i) or formula (ii) in the _{- ((CH 2) y CH} 2 O) - or _{- ((CH 2) y CH} (CH 3) O) - , the oxygen atom side ends Is preferred in which X is bonded to X.

  The compounds represented by the general formula (i) or (ii) may be used alone or in combination of two or more. In particular, in the general formula (ii), a form in which all six Xs are acryloyl groups is preferable.

  The compound represented by the general formula (i) or (ii) is a ring-opening skeleton by a ring-opening addition reaction of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol, which is a conventionally known process. And a step of reacting, for example, (meth) acryloyl chloride with the terminal hydroxyl group of the ring-opening skeleton to introduce a (meth) acryloyl group. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (i) or (ii).

Among the compounds represented by the general formula (i) or (ii), a pentaerythritol derivative and / or a dipentaerythritol derivative is more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), and among them, exemplary compounds (a) and ( b), (e) and (f) are preferred.

  Examples of commercially available products such as polymerizable monomers represented by general formulas (i) and (ii) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy chains.

Examples of polymerizable monomers include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Furthermore, as polymerizable monomers, addition polymerizable monomers having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, JP-A-1-105238 Can be used to obtain a curable composition having a very high photosensitive speed.
Commercially available products such as polymerizable monomers include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA -306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.

  A polyfunctional thiol compound having two or more mercapto (SH) groups in the same molecule is also suitable as the polymerizable monomer. Particularly preferred are those represented by the following general formula (I).

(In the formula, R ¹ is an alkyl group, R ² is an n-valent aliphatic group that may contain atoms other than carbon, R ⁰ is an alkyl group that is not H, and n represents 2 to 4).

  If the polyfunctional thiol compound represented by the general formula (I) is specifically exemplified, 1,4-bis (3-mercaptobutyryloxy) butane [formula (II)] having the following structural formula: 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triasian-2,4,6 (1H, 3H5H) -trione [formula (III)] and pentaerythritol tetrakis (3 -Mercaptobutyrate) [formula (IV)] and the like. These polyfunctional thiols can be used alone or in combination.

  In the present invention, it is also preferable to use a polymerizable monomer or oligomer having two or more epoxy groups or oxetanyl groups in the molecule as the polymerizable monomer. Specific examples of these will be described collectively in the column of the compound having an epoxy group or oxetanyl group described later.

<< B: polymer having a polymerizable group in the side chain >>
The 2nd preferable aspect of the composition of this invention is an aspect containing the polymer which has a polymeric group in a side chain as a polymeric compound.
Examples of the polymerizable group include an ethylenically unsaturated double bond group, an epoxy group, and an oxetanyl group.
The latter is described collectively in the column of the compound having an epoxy group or oxetanyl group described later.

  The polymer having an ethylenically unsaturated bond in the side chain is a high polymer having at least one selected from functional groups represented by any one of the following general formulas (1) to (3) as an unsaturated double bond moiety. Molecular compounds are preferred.

In the general formula (1), R ^{1 to} R ³ each independently represent a hydrogen atom or a monovalent organic group, and R ¹ is preferably a hydrogen atom or an alkyl which may have a substituent. A hydrogen atom and a methyl group are preferable because of high radical reactivity. R ² and R ³ are each independently a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an optionally substituted alkyl group, or a substituted group. An aryl group that may have a group, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylamino group that may have a substituent, and a substituent An arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, a substituent An alkyl group which may have a substituent and an aryl group which may have a substituent are preferable because of high radical reactivity.

X represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —, and R ¹² represents a hydrogen atom or a monovalent organic group. Here, examples of R ¹² include an alkyl group which may have a substituent. Among them, a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.

  Here, examples of the substituent that can be introduced include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, an alkylamino group, an arylamino group, a carboxyl group, an alkoxycarbonyl group, A sulfo group, a nitro group, a cyano group, an amide group, an alkylsulfonyl group, an arylsulfonyl group and the like can be mentioned.

In the general formula (2), R ^{4 to} R ⁸ each independently represents a hydrogen atom or a monovalent organic group, and R ^{4 to} R ⁸ are preferably a hydrogen atom, a halogen atom, an amino group, or a dialkyl. Amino group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy which may have a substituent A group, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, Examples include an arylsulfonyl group which may have a substituent. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl which may have a substituent Groups are preferred.

Examples of the substituent that can be introduced are the same as those in the general formula (1). Y represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —. R ¹² has the same meaning as R ¹² in general formula (1), and preferred examples are also the same.

In the general formula (3), R ⁹ is preferably a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom or a methyl group has high radical reactivity. To preferred. R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or an alkyl group which may have a substituent. An aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, a substituent An arylamino group that may have, an alkylsulfonyl group that may have a substituent, an arylsulfonyl group that may have a substituent, and the like, among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, An alkyl group which may have a substituent and an aryl group which may have a substituent are preferable because of high radical reactivity.

Here, examples of the substituent that can be introduced are the same as those in the general formula (1). Further, Z is an oxygen atom, a sulfur atom, -N (R ¹³⁾ -, or a phenylene group which may have a substituent. Examples of R ¹³ include an alkyl group which may have a substituent. Among them, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.

  As the polymer containing an ethylenically unsaturated bond in the side chain in the present invention, the structural unit containing the functional group represented by the general formulas (1) to (3) is contained in an amount of 20 mol% to 95 mol in one molecule. It is preferable that it is a compound containing in less than%. More preferably, it is 25-90 mol%. More preferably, it is the range of 30 mol% or more and less than 85 mol%.

  The synthesis of the polymer compound having a structural unit containing a group represented by the general formulas (1) to (3) is a synthesis method described in paragraphs [0027] to [0057] of JP-A No. 2003-262958. Can be done on the basis of Of these, the synthesis method 1) in the publication is preferred.

The polymer having an ethylenically unsaturated bond used in the present invention may further have an acid group.
The acid group in the present application has a dissociable group having a pKa of 14 or less. Specifically, for example, —COOH, —SO ₃ H, —PO ₃ H ₂ , —OSO ₃ H, —OPO ₂ H _{2, -PhOH, -SO 2 H,} -SO 2 NH 2, -SO 2 NHCO -, - SO 2 NHSO 2 - and the like, among -COOH, -SO ₃ H, is -PO ₃ H ₂ preferably , -COOH is more preferred.

  A polymer containing an acid group and an ethylenically unsaturated bond in the side chain can be obtained, for example, by adding an ethylenically unsaturated group-containing epoxy compound to the carboxyl group of an alkali-soluble polymer having a carboxyl group.

  As a polymer having a carboxyl group, 1) a polymer obtained by radical polymerization or ion polymerization of a monomer having a carboxyl group, and 2) radical or ion polymerization of a monomer having an acid anhydride to hydrolyze or half-esterify an acid anhydride unit. 3) Epoxy acrylate obtained by modifying an epoxy polymer with an unsaturated monocarboxylic acid and an acid anhydride.

  Specific examples of vinyl polymers having a carboxyl group include (meth) acrylic acid, 2-succinoloyloxyethyl methacrylate, 2-malenoyloxyethyl methacrylate, and methacrylic acid 2 as monomers having a carboxyl group. -Polymers obtained by homopolymerizing unsaturated carboxylic acids such as phthaloyloxyethyl, 2-hexahydrophthaloyloxyethyl methacrylate, maleic acid, fumaric acid, itaconic acid, and crotonic acid, and these unsaturated carboxylic acids as styrene , Α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, vinyl acetate, acrylonitrile, (meth) acrylamide , Glycidyl (meth) acryl , Allyl glycidyl ether, glycidyl ethyl acrylate, glycidyl crotonic acid ether, (meth) acrylic acid chloride, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-methylolacrylamide, N, N-dimethylacrylamide, N -A polymer copolymerized with a vinyl monomer having no carboxyl group, such as methacryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, and N, N-dimethylaminoethylacrylamide.

  In addition, maleic anhydride is copolymerized with styrene, α-methylstyrene, etc., and the maleic anhydride unit part is half-esterified with monohydric alcohol such as methanol, ethanol, propanol, butanol, hydroxyethyl (meth) acrylate, or water. Also included are hydrolyzed polymers.

  Among the above, a polymer having a carboxyl group, in particular, a (meth) acrylic acid (co) polymer containing (meth) acrylic acid is preferable, and specific examples of these copolymers include, for example, Methyl methacrylate / methacrylic acid copolymer described in JP-A-60-208748, Methyl methacrylate / methyl acrylate / methacrylic acid copolymer described in JP-A-60-214354, JP-A-5-36581 Benzyl methacrylate / methyl methacrylate / methacrylic acid / 2-ethylhexyl acrylate copolymer described in JP-A-5-333542, methyl methacrylate / n-butyl methacrylate / 2-ethylhexyl acrylate / methacrylic acid copolymer Polymer, styrene / methyl methacrylate described in JP-A-7-261407 Methyl acrylate / methacrylic acid copolymer, methyl methacrylate / n-butyl acrylate / 2-ethylhexyl acrylate / methacrylic acid copolymer described in JP-A-10-110008, and JP-A-10-198031 Examples thereof include methyl methacrylate / n-butyl acrylate / 2-ethylhexyl acrylate / styrene / methacrylic acid copolymer.

  The polymer containing an acid group and a polymerizable group in the side chain in the present invention is a structural unit represented by any one of the following general formulas (1-1) to (3-1) as an unsaturated double bond moiety. A polymer compound having at least one selected is preferable.

In the general formulas (1-1) to (3-1), A ¹ , A ² , and A ³ each independently represent an oxygen atom, a sulfur atom, or —N (R ²¹ ) —, and R ²¹ Represents an alkyl group which may have a substituent. G ¹ , G ² , and G ³ each independently represent a divalent organic group. X and Z each independently represent an oxygen atom, a sulfur atom, or —N (R ²² ) —, and R ²² represents an alkyl group which may have a substituent. Y represents an oxygen atom, a sulfur atom, a phenylene group which may have a substituent, or —N (R ²³ ) —, and R ²³ represents an alkyl group which may have a substituent. R ^{1 to} R ²⁰ each independently represents a monovalent substituent.

In the general formula (1-1), R ^{1 to} R ³ each independently represents a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may further have a substituent. R ¹ and R ² are preferably a hydrogen atom, and R ³ is preferably a hydrogen atom or a methyl group.
R ^{4 to} R ⁶ each independently represents a monovalent substituent. Examples of R ⁴ include a hydrogen atom or an alkyl group which may further have a substituent. Among them, a hydrogen atom, a methyl group An ethyl group is preferred. R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group that may further have a substituent, or a substituent. An aryl group which may further have a substituent, an aryloxy group which may further have a substituent, an alkylsulfonyl group which may further have a substituent, and further having a substituent An arylsulfonyl group which may be substituted may be mentioned. Among them, a hydrogen atom, an alkoxycarbonyl group, an alkyl group which may further have a substituent, and an aryl group which may further have a substituent are preferable.
Here, examples of the substituent that can be introduced include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group, a methyl group, an ethyl group, and a phenyl group.

A ¹ represents an oxygen atom, a sulfur atom, or —N (R ²¹ ) —, and X represents an oxygen atom, a sulfur atom, or —N (R ²² ) —. Here, examples of R ²¹ and R ²² include an alkyl group which may have a substituent.
G ¹ represents a divalent organic group, but an alkylene group which may have a substituent is preferable. More preferably, it has an alkylene group which may have a substituent having 1 to 20 carbon atoms, a cycloalkylene group which may have a substituent having 3 to 20 carbon atoms, or a substituent having 6 to 20 carbon atoms. An aromatic group that may be present may be mentioned. Among them, a linear or branched alkylene group having 1 to 10 carbon atoms that may have a substituent, or cyclo that may have a substituent having 3 to 10 carbon atoms. An alkylene group and an aromatic group which may have a substituent having 6 to 12 carbon atoms are preferable in terms of performance such as strength and developability.
Here, a hydroxyl group is preferable as a substituent in G ¹ .

In the general formula (2-1), R ^{7 to} R ⁹ each independently represents a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may further have a substituent. R ⁷ and R ⁸ are preferably a hydrogen atom, and R ⁹ is preferably a hydrogen atom or a methyl group.
R ^{10 to} R ¹² each independently represents a monovalent substituent. Specific examples of the substituent include a hydrogen atom, a halogen atom, a dialkylamino group, an alkoxycarbonyl group, a sulfo group, and a nitro group. , A cyano group, an alkyl group which may further have a substituent, an aryl group which may further have a substituent, an alkoxy group which may further have a substituent, and an aryl which may further have a substituent Examples thereof include an oxy group, an alkylsulfonyl group that may further have a substituent, and an arylsulfonyl group that may further have a substituent. Among them, a hydrogen atom, an alkoxycarbonyl group, and a substituent may be further included. A good alkyl group and an aryl group which may further have a substituent are preferred.
Here, examples of the substituent that can be introduced include those exemplified in the general formula (1-1).

A ² each independently represents an oxygen atom, a sulfur atom, or —N (R ²¹ ) —, wherein R ²¹ is a hydrogen atom, an alkyl group which may have a substituent, or the like. Can be mentioned.
G ² represents a divalent organic group, and an alkylene group which may have a substituent is preferable. Preferably, it has an alkylene group which may have a substituent having 1 to 20 carbon atoms, a cycloalkylene group which may have a substituent having 3 to 20 carbon atoms, and a substituent which has 6 to 20 carbon atoms. Aromatic group, etc. may be mentioned. Among them, a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, or a cycloalkylene which may have a substituent having 3 to 10 carbon atoms. Group, and an aromatic group which may have a substituent having 6 to 12 carbon atoms is preferable in terms of performance such as strength and developability.
Here, the substituent in G ² is preferably a hydroxyl group.

Y represents an oxygen atom, a sulfur atom, —N (R ²³ ) — or a phenylene group which may have a substituent. Here, examples of R ²³ include a hydrogen atom and an alkyl group which may have a substituent.

In the general formula (3-1), R ^{13 to} R ¹⁵ each independently represents a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may have a substituent. ¹³ and R ¹⁴ are preferably hydrogen atoms, and R ¹⁵ is preferably a hydrogen atom or a methyl group.
R ^{16 to} R ²⁰ each independently represents a monovalent substituent. R ^{16 to} R ²⁰ are, for example, a hydrogen atom, a halogen atom, a dialkylamino group, an alkoxycarbonyl group, a sulfo group, a nitro group, or a cyano group. , An alkyl group that may further have a substituent, an aryl group that may further have a substituent, an alkoxy group that may further have a substituent, an aryloxy group that may further have a substituent, Examples include an alkylsulfonyl group that may further have a substituent, an arylsulfonyl group that may further have a substituent, and the like. Among them, a hydrogen atom, an alkoxycarbonyl group, and an alkyl group that may further have a substituent An aryl group which may further have a substituent is preferable. Examples of the substituent that can be introduced include those listed in the general formula (1).
A ³ represents an oxygen atom, a sulfur atom, or —N (R ²¹ ) —, and Z represents an oxygen atom, a sulfur atom, or —N (R ²² ) —. Examples of R ²¹ and R ²² include the same as those in the general formula (1).

G ³ represents a divalent organic group, but an alkylene group which may have a substituent is preferable. Preferably, it has an alkylene group which may have a substituent having 1 to 20 carbon atoms, a cycloalkylene group which may have a substituent having 3 to 20 carbon atoms, and a substituent which has 6 to 20 carbon atoms. Aromatic group, etc. may be mentioned. Among them, a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, or a cycloalkylene which may have a substituent having 3 to 10 carbon atoms. Group, and an aromatic group which may have a substituent having 6 to 12 carbon atoms is preferable in terms of performance such as strength and developability.
Here, the substituent in G ³ is preferably a hydroxyl group.

  Preferred examples of the structural unit having an ethylenically unsaturated bond and an acid group include the following polymer compounds 1 to 17.

  The polymer containing an acid group and an ethylenically unsaturated bond in the side chain in the present invention preferably has an acid value in the range of 20 to 300, preferably 40 to 200, more preferably 60 to 150.

The polymer having a polymerizable group in the side chain used in the present invention is also preferably a polymer having an ethylenically unsaturated bond and a urethane group in the side chain (hereinafter sometimes referred to as “urethane polymer”).
The urethane polymer has a structural unit represented by a reaction product of at least one diisocyanate compound represented by the following general formula (4) and at least one diol compound represented by the general formula (5). A polyurethane polymer having a basic skeleton (hereinafter referred to as “specific polyurethane polymer” as appropriate).

OCN-X ⁰ -NCO General formula (4)
HO—Y ⁰ —OH Formula (5)

In general formulas (4) and (5), X ⁰ and Y ⁰ each independently represent a divalent organic residue.

  At least one of the diisocyanate compound represented by the general formula (4) or the diol compound represented by the general formula (5) represents the general formulas (1) to (3) indicating the unsaturated double bond portion. Group represented by the general formulas (1) to (3) in the side chain as a reaction product of the diisocyanate compound and the diol compound. A specific polyurethane polymer in which is introduced is produced. According to this method, the specific polyurethane polymer according to the present invention can be produced more easily than the substitution and introduction of a desired side chain after the reaction of the polyurethane polymer.

1) Diisocyanate compound The diisocyanate compound represented by the general formula (4) is obtained by, for example, subjecting a triisocyanate compound to 1 equivalent of a monofunctional alcohol or monofunctional amine compound having an unsaturated group. There are products that are produced.
Examples of the triisocyanate compound include those shown below, but are not limited thereto.

  Examples of the monofunctional alcohol or monofunctional amine compound having an unsaturated group include those shown below, but are not limited thereto.

  Here, as a method for introducing an unsaturated group into the side chain of the polyurethane polymer, a method using a diisocyanate compound containing an unsaturated group in the side chain as a raw material for producing the polyurethane polymer is suitable. Examples of the diisocyanate compound obtained by addition reaction of a triisocyanate compound and a monofunctional alcohol having an unsaturated group or 1 equivalent of a monofunctional amine compound having an unsaturated group in the side chain include, for example, Although the following are mentioned, it is not limited to this.

  The specific polyurethane polymer used in the present invention includes, for example, the above-mentioned diisocyanate compound containing an unsaturated group from the viewpoint of improving compatibility with other components in the polymerizable composition and improving storage stability. Other diisocyanate compounds can be copolymerized.

  Examples of the diisocyanate compound to be copolymerized include the following. Preferred is a diisocyanate compound represented by the following general formula (6).

OCN-L ¹ -NCO the general formula (6)

In General Formula (6), L ¹ represents a divalent aliphatic or aromatic hydrocarbon group which may have a substituent. If necessary, L ¹ may have another functional group that does not react with an isocyanate group, such as an ester, urethane, amide, or ureido group.

Specific examples of the diisocyanate compound represented by the general formula (6) include those shown below.
That is, 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate Aromatic diisocyanate compounds such as 1,5-naphthylene diisocyanate, 3,3′-dimethylbiphenyl-4,4′-diisocyanate;
Aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate and the like;
Alicyclic diisocyanate compounds such as isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane;
And a diisocyanate compound which is a reaction product of a diol and a diisocyanate such as an adduct of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate.

2) Diol Compound As the diol compound represented by the general formula (5), a polyether diol compound, a polyester diol compound, a polycarbonate diol compound, and the like are widely used.

  Here, as a method for introducing an unsaturated group into the side chain of the polyurethane polymer, in addition to the above-described method, a method using a diol compound containing an unsaturated group in the side chain as a raw material for producing the polyurethane polymer is also suitable. is there. Such a diol compound may be a commercially available one such as trimethylolpropane monoallyl ether, a halogenated diol compound, a triol compound, an aminodiol compound, a carboxylic acid containing an unsaturated group, and an acid. It may be a compound that is easily produced by a reaction with a chloride, isocyanate, alcohol, amine, thiol, or alkyl halide compound. Specific examples of these compounds include, but are not limited to, the compounds shown below.

  Further, as a more preferred polymer in the present invention, a polyurethane obtained by using a diol compound represented by the following general formula (G) as at least one diol compound having an ethylenically unsaturated bond group in the synthesis of polyurethane. You can list trees.

In the general formula (G), R ^{1 to} R ³ each independently represents a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom, or — N (R ¹² ) — is represented, and R ¹² represents a hydrogen atom or a monovalent organic group.
Incidentally, R ¹ to R ³ and X in the general formula (G) has the same meaning as R ¹ to R ³ and X in the general formula (1), preferred embodiments versa.
By using a polyurethane polymer derived from such a diol compound, it is considered that the coating strength of the layer can be improved by suppressing the excessive molecular motion of the polymer main chain caused by the secondary alcohol having a large steric hindrance. It is done.
Hereinafter, specific examples of the diol compound represented by the general formula (G) which are suitably used for the synthesis of the specific polyurethane polymer will be shown.

The specific polyurethane polymer used in the present invention is, for example, the above-mentioned diol compound containing an unsaturated group from the viewpoint of improving compatibility with other components in the polymerizable composition and improving storage stability. Diol compounds other than can be copolymerized.
Examples of such diol compounds include the polyether diol compounds, polyester diol compounds, and polycarbonate diol compounds described above.

  Examples of the polyether diol compound include compounds represented by the following formulas (7), (8), (9), (10), and (11), and random copolymerization of ethylene oxide and propylene oxide having a hydroxyl group at the terminal. Coalescence is mentioned.

In formulas (7) to (11), R ¹⁴ represents a hydrogen atom or a methyl group, and X ¹ represents the following group. Moreover, a, b, c, d, e, f, and g each represent an integer of 2 or more, and preferably an integer of 2 to 100.

Specific examples of the polyether diol compound represented by the above formulas (7) and (8) include the following.
That is, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, di-1,2-propylene glycol, tri-1,2-propylene glycol, tetra-1, 2-propylene glycol, hexa-1,2-propylene glycol, di-1,3-propylene glycol, tri-1,3-propylene glycol, tetra-1,3-propylene glycol, di-1,3-butylene glycol, Tri-1,3-butylene glycol, hexa-1,3-butylene glycol, polyethylene glycol having a weight average molecular weight of 1000, polyethylene glycol having a weight average molecular weight of 1500, poly having a weight average molecular weight of 2000 Tylene glycol, polyethylene glycol with a weight average molecular weight of 3000, polyethylene glycol with a weight average molecular weight of 7500, polypropylene glycol with a weight average molecular weight of 400, polypropylene glycol with a weight average molecular weight of 700, polypropylene glycol with a weight average molecular weight of 1000, polypropylene glycol with a weight average molecular weight of 2000 , Polypropylene glycol having a weight average molecular weight of 3000, polypropylene glycol having a weight average molecular weight of 4000, and the like.

Specific examples of the polyether diol compound represented by the formula (9) include those shown below.
That is, Sanyo Chemical Industries, Ltd. (trade name) PTMG650, PTMG1000, PTMG2000, PTMG3000, and the like.

Specific examples of the polyether diol compound represented by the formula (10) include those shown below.
That is, Sanyo Chemical Industries, Ltd. (trade name) New Pole PE-61, New Pole PE-62, New Pole PE-64, New Pole PE-68, New Pole PE-71, New Pole PE-74, New Pole PE-75, New Pole PE-78, New Pole PE-108, New Pole PE-128, New Pole PE-61, and the like.

Specific examples of the polyether diol compound represented by the formula (11) include those shown below.
That is, Sanyo Chemical Industries, Ltd. (trade name) New Pole BPE-20, New Pole BPE-20F, New Pole BPE-20NK, New Pole BPE-20T, New Pole BPE-20G, New Pole BPE-40, New Pole BPE-60, New Pole BPE-100, New Pole BPE-180, New Pole BPE-2P, New Pole BPE-23P, New Pole BPE-3P, New Pole BPE-5P, and the like.

Specific examples of the random copolymer of ethylene oxide and propylene oxide having a hydroxyl group at the terminal include the following.
That is, Sanyo Chemical Industries, Ltd. (trade name) New Pole 50HB-100, New Pole 50HB-260, New Pole 50HB-400, New Pole 50HB-660, New Pole 50HB-2000, New Pole 50HB-5100, etc. It is.

  Examples of the polyester diol compound include compounds represented by formulas (12) and (13).

In formulas (12) and (13), L ² , L ³ and L ⁴ may be the same or different and each represents a divalent aliphatic or aromatic hydrocarbon group, and L ⁵ represents a divalent aliphatic carbonization. Represents a hydrogen group. Preferably, L ^{2 to} L ⁴ each represent an alkylene group, an alkenylene group, an alkynylene group, or an arylene group, and L ⁵ represents an alkylene group. In addition, other functional groups that do not react with the isocyanate group, such as ether, carbonyl, ester, cyano, olefin, urethane, amide, ureido group, or halogen atom may be present in L ^{2 to} L ⁵ . n1 and n2 are each an integer of 2 or more, preferably an integer of 2 to 100.
As the polycarbonate diol compound, there is a compound represented by the formula (14).

In the formula (14), L ⁶ may be the same or different and each represents a divalent aliphatic or aromatic hydrocarbon group. Preferably, L ⁶ represents an alkylene group, an alkenylene group, an alkynylene group or an arylene group. In addition, other functional groups that do not react with the isocyanate group, such as ether, carbonyl, ester, cyano, olefin, urethane, amide, ureido group or halogen atom may be present in L ⁶ . n3 is an integer of 2 or more, and preferably represents an integer of 2 to 100.

  Specific examples of the diol compound represented by the above formula (12), (13) or (14) include (Exemplary Compound No. 1) to (Exemplary Compound No. 18) shown below. N in the specific examples represents an integer of 2 or more.

  Moreover, in the synthesis | combination of a specific polyurethane polymer, the diol compound which has a substituent which does not react with an isocyanate group other than the said diol compound can also be used together. Examples of such diol compounds include those shown below.

^{HO-L 7 -O-CO-} L 8 -CO-O-L 7 -OH (15)
^{HO-L 8 -CO-O-} L 7 -OH (16)

In the formulas (15) and (16), L ⁷ and L ⁸ may be the same or different, and each may have a substituent (for example, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, —F, — And a divalent aliphatic hydrocarbon group, aromatic hydrocarbon group or heterocyclic group which may have a halogen atom such as Cl, -Br and -I. If necessary, L ⁷ and L ⁸ may have another functional group that does not react with an isocyanate group, such as a carbonyl group, an ester group, a urethane group, an amide group, or a ureido group. Note that L ⁷ and L ⁸ may form a ring.

Furthermore, in the synthesis of the specific polyurethane polymer, a diol compound having a carboxyl group can be used in combination with the diol compound.
Examples of such diol compounds include those represented by the following formulas (17) to (19).

In the formulas (17) to (19), R ¹⁵ is a hydrogen atom, a substituent (for example, a halogen atom such as a cyano group, a nitro group, —F, —Cl, —Br, —I, etc.), —CONH ₂ , —COOR ^16. , -OR ¹⁶ , -NHCONHR ¹⁶ , -NHCONOR ¹⁶ , -NHCOR ¹⁶ , -OCONHR ¹⁶ (wherein R ¹⁶ represents an alkyl group having 1 to 10 carbon atoms and an aralkyl group having 7 to 15 carbon atoms). Represents an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or an aryloxy group, which may have a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or 6 to 6 carbon atoms. Represents 15 aryl groups. L ⁹ , L ¹⁰ and L ¹¹ may be the same or different from each other, and may have a single bond or a substituent (for example, alkyl, aralkyl, aryl, alkoxy and halogeno groups are preferred). Represents a divalent aliphatic or aromatic hydrocarbon group, preferably an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms. . If necessary, L ^{9 to} L ¹¹ may have other functional groups that do not react with isocyanate groups, such as carbonyl, ester, urethane, amide, ureido, and ether groups. A ring may be formed by 2 or 3 of R ¹⁵ , L ⁷ , L ⁸ and L ⁹ .
Ar represents a trivalent aromatic hydrocarbon group which may have a substituent, and preferably represents an aromatic group having 6 to 15 carbon atoms.

Specific examples of the diol compound having a carboxyl group represented by the above formulas (17) to (19) include those shown below.
3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, Bis (hydroxymethyl) acetic acid, bis (4-hydroxyphenyl) acetic acid, 2,2-bis (hydroxymethyl) butyric acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine N, N-bis (2-hydroxyethyl) -3-carboxy-propionamide and the like.

  The presence of such a carboxyl group is preferable because the polyurethane polymer can be provided with properties such as hydrogen bonding properties and alkali solubility. More specifically, the polyurethane polymer having an ethylenically unsaturated bond group in the side chain is a polymer further having a carboxyl group in the side chain, and more specifically, an ethylenically unsaturated bond group in the side chain. A polyurethane polymer having 0.3 meq / g or more and having a carboxyl group in the side chain of 0.4 meq / g or more is particularly preferably used as the binder polymer of the present invention.

  In addition to the diol, a compound obtained by ring-opening a tetracarboxylic dianhydride represented by the following formulas (20) to (22) with a diol compound may be used in combination with the synthesis of the specific polyurethane polymer. it can.

In formulas (20) to (22), L ¹² may have a single bond or a substituent (for example, alkyl, aralkyl, aryl, alkoxy, halogeno, ester, or amide groups are preferred). Represents an aliphatic or aromatic hydrocarbon group, —CO—, —SO—, —SO ₂ —, —O— or S—, preferably a single bond and a divalent aliphatic carbon having 1 to 15 carbon atoms. hydrogen _{group, -CO -, - SO 2 -} , - represents O- or S- to. R ¹⁷ and R ¹⁸ may be the same or different and each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or a halogeno group, preferably a hydrogen atom or an alkyl having 1 to 8 carbon atoms. Group, an aryl group having 6 to 15 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a halogeno group. Two of L ¹² , R ¹⁷ and R ¹⁸ may be bonded to form a ring.

R ¹⁹ and R ²⁰ may be the same or different and each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a halogeno group, preferably a hydrogen atom, an alkyl having 1 to 8 carbon atoms, or a carbon number of 6 Represents ~ 15 aryl groups. Two of L ¹² , R ¹⁹ and R ²⁰ may be bonded to form a ring. L ¹³ and L ¹⁴ may be the same or different and each represents a single bond, a double bond, or a divalent aliphatic hydrocarbon group, and preferably represents a single bond, a double bond, or a methylene group. A represents a mononuclear or polynuclear aromatic ring. Preferably, it represents an aromatic ring having 6 to 18 carbon atoms.

Specific examples of the compound represented by the above formula (20), (21) or (22) include those shown below.
That is, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride, 2,3,6 , 7-Naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4′-sulfonyldiphthalic dianhydride, 2,2-bis (3,4 Dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 4,4 ′-[3,3 ′-(alkylphosphoryldiphenylene) -bis (iminocarbonyl)] diphthalic acid Dianhydride,

Aromatic tetracarboxylic dianhydrides such as adducts of hydroquinone diacetate and trimetic anhydride, diacetyldiamine and trimetic anhydride; 5- (2,5-dioxotetrahydrofuryl) -3-methyl- 3-cyclohexsi-1,2-dicarboxylic anhydride (Dainippon Ink Chemical Co., Ltd., Epicron B-4400), 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2 Alicyclic tetracarboxylic dianhydrides such as 1,4,5-cyclohexanetetracarboxylic dianhydride, tetrahydrofuran tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1, Aliphatic tetracarboxylic dianhydrides such as 2,4,5-pentanetetracarboxylic dianhydride may be mentioned.

Examples of a method for introducing a compound obtained by ring-opening these tetracarboxylic dianhydrides with a diol compound into a polyurethane polymer include the following methods.
a) A method of reacting an alcohol-terminated compound obtained by ring-opening tetracarboxylic dianhydride with a diol compound and a diisocyanate compound.
b) A method of reacting an alcohol-terminated urethane compound obtained by reacting a diisocyanate compound under an excess of a diol compound with tetracarboxylic dianhydride.

Specific examples of the diol compound used for the ring-opening reaction include those shown below.
That is, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butylene glycol, 1,6-hexanediol, 2-butene- 1,4-diol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-bis-β-hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclodecane dimethanol, hydrogenated bisphenol A, hydrogenated Bisphenol F, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, bisphenol F ethylene oxide adduct, bisphenol F pro Renoxide adduct, hydrogenated bisphenol A ethylene oxide adduct, hydrogenated bisphenol A propylene oxide adduct, hydroquinone dihydroxyethyl ether, p-xylylene glycol, dihydroxyethyl sulfone, bis (2-hydroxyethyl) -2, Examples include 4-tolylene dicarbamate, 2,4-tolylene-bis (2-hydroxyethylcarbamide), bis (2-hydroxyethyl) -m-xylylenedicarbamate, and bis (2-hydroxyethyl) isophthalate.

The specific polyurethane polymer that can be used in the present invention is synthesized by adding the above-mentioned diisocyanate compound and diol compound to an aprotic solvent by adding a known catalyst having an activity corresponding to each reactivity and heating. The molar ratio (M _a : M _b ) of the diisocyanate and diol compound used in the synthesis is preferably 1: 1 to 1.2: 1, and the molecular weight or viscosity is desired by treating with alcohols or amines. The product having the physical properties is finally synthesized in a form in which no isocyanate group remains.

  As an introduction amount of the ethylenically unsaturated bond contained in the specific polyurethane polymer according to the present invention, in terms of equivalent, 0.3 meq / g or more of an ethylenically unsaturated bond group in the side chain, and further 0.35 to It is preferable to contain 1.50 meq / g.

  The molecular weight of the specific polyurethane polymer according to the present invention is preferably 10,000 or more in terms of weight average molecular weight, and more preferably in the range of 40,000 to 200,000.

  In the present invention, a styrene polymer having an ethylenically unsaturated bond in the side chain (hereinafter sometimes referred to as “styrene polymer”) is also preferable, and a styrenic double bond (styrene) represented by the following general formula (23): And α-methylstyrene-based double bond) and those having at least one of vinylpyridinium groups represented by the following general formula (24) are more preferable.

In the general formula (23), R ²¹ represents a hydrogen atom or a methyl group. R ²² represents any substitutable atom or atomic group. k represents an integer of 0 to 4.
In addition, the styrenic double bond represented by the general formula (23) is connected to the polymer main chain through a single bond or a connecting group consisting of an arbitrary atom or atomic group, and the way of bonding is particularly There is no limit.
Although the preferable example is shown as a repeating unit of the high molecular compound which has a functional group represented by General formula (23) below, this invention is not limited to these examples.

In the general formula (24), R ²³ represents a hydrogen atom or a methyl group. R ²⁴ represents any substitutable atom or atomic group. m represents an integer of 0 to 4. A ⁻ represents an anion. Further, the pyridinium ring may take the form of benzopyridinium fused with a benzene ring as a substituent, and in this case includes a quinolium group and an isoquinolium group.
The vinylpyridinium group represented by the general formula (24) is connected to the polymer main chain through a single bond or a connecting group consisting of an arbitrary atom or atomic group, and there is no particular limitation on the way of bonding. Absent.
Although the preferable example is shown below as a repeating unit of the high molecular compound which has a functional group represented by General formula (24) below, this invention is not limited to these examples.

  One of the methods for synthesizing the styrenic polymer is a monomer having a functional group represented by the general formula (23) or (24) and having a functional group copolymerizable with another copolymer component. The method of copolymerizing each other using a well-known copolymerization method is mentioned. Here, the styrenic polymer may be a homopolymer having only one of the functional groups represented by the general formulas (23) and (24), or either one or A copolymer having two or more types of both functional groups may be used.

  Further, it may be a copolymer with other copolymerization monomers not containing these functional groups. As another copolymerization monomer in this case, it is preferable to select a carboxy group-containing monomer, for example, for the purpose of imparting solubility to an aqueous alkaline solution to the polymer. Acrylic acid, methacrylic acid, acrylic acid 2-carboxyethyl ester Examples thereof include 2-carboxyethyl methacrylate, crotonic acid, maleic acid, fumaric acid, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like.

  In addition to the monomer having a carboxy group, other monomer components may be introduced into the copolymer to be synthesized and used as a (multi-component) copolymer. In such cases, monomers that can be incorporated into the copolymer include styrene, 4-methylstyrene, 4-hydroxystyrene, 4-acetoxystyrene, 4-carboxystyrene, 4-aminostyrene, chloromethylstyrene, and 4-methoxystyrene. Styrene derivatives such as, vinylphosphonic acid, vinylsulfonic acid and salts thereof, styrenesulfonic acid and salts thereof, 4-vinylpyridine, 2-vinylpyridine, N-vinylimidazole, N-vinylcarbazole, 4-vinylbenzyltrimethylammonium chloride Quaternized product of N-vinylimidazole with methyl chloride, 4-vinylbenzylpyridinium chloride, acrylonitrile, methacrylonitrile, phenylmaleimide, hydroxyphenylmaleimide, vinyl acetate, Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, vinyl benzoate, vinyl ethers such as methyl vinyl ether, butyl vinyl ether, N-vinylpyrrolidone, acryloylmorpholine, vinyl chloride, vinylidene chloride, allyl alcohol Various monomers such as vinyltrimethoxysilane are appropriately used as copolymerization monomers.

  When using the above-mentioned copolymer as the styrenic polymer, the proportion of the repeating unit having the functional group represented by the general formula (23) and / or the general formula (24) in the entire copolymer composition Is preferably 20% by mass or more, and more preferably 40% by mass or more. Within this range, the effect of the present invention is excellent and a highly sensitive crosslinking system is provided.

  The molecular weight of the styrenic polymer is preferably in the range of 10,000 to 300,000 in terms of weight average molecular weight, more preferably in the range of 15,000 to 200,000, and most preferably in the range of 20000 to 150,000.

As other polymers having an ethylenically unsaturated bond in the side chain, as novolak polymers having an ethylenically unsaturated group in the side chain, for example, the polymers described in JP-A-9-269596, Examples thereof include a polymer in which an ethylenically unsaturated bond is introduced into a side chain using the method described in Japanese Patent No. 62648.
Moreover, as an acetal polymer which has an ethylenically unsaturated bond in a side chain, the polymer etc. which are described in Unexamined-Japanese-Patent No. 2002-162741 are mentioned, for example.
Furthermore, as the polyamide-based polymer having an ethylenically unsaturated bond in the side chain, for example, the polymer described in Japanese Patent Application No. 2003-321022 or the polyamide polymer cited therein is disclosed in JP-A-2002-62648. Examples thereof include a polymer having an ethylenically unsaturated bond introduced into the side chain by the described method.
Examples of the polyimide polymer having an ethylenically unsaturated bond in the side chain include, for example, a polymer described in Japanese Patent Application No. 2003-339785, or a polyimide polymer cited therein, and a method described in JP-A-2002-62648. And polymers having an ethylenically unsaturated bond introduced in the side chain.

<< C: Compound having epoxy group or oxetanyl group >>
The 3rd preferable aspect of this invention is an aspect containing the compound which has an epoxy group or an oxetanyl group as a polymeric compound. Specific examples of the compound having an epoxy group or oxetanyl group include a polymer having an epoxy group in the side chain, and a polymerizable monomer or oligomer having two or more epoxy groups in the molecule, and a bisphenol A type epoxy resin, Bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like can be mentioned.
These compounds may be used as commercial products or can be obtained by introducing an epoxy group into the side chain of the polymer.

  As a commercial product, for example, as bisphenol A type epoxy resin, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (manufactured by DIC Corporation), etc., and bisphenol F type epoxy resin is JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835. (Above, manufactured by DIC Corporation), LCE-21, RE-602S (above, Nippon Kayaku) As a phenol novolac type epoxy resin, JER152, JER154, JER157S70, JER157S65 (manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N- 770, EPICLON N-775 (manufactured by DIC Corporation) and the like, and cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N- 680, EPICLON N-690, EPICLON N-695 (manufactured by DIC Corporation), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), etc., and as an aliphatic epoxy resin, ADEK RESIN EP-4080S, EP-4085S, EP-4088S (above, manufactured by ADEKA) Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (above, Daicel Chemical Industries) (Manufactured by Nagase ChemteX Corporation), etc., Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Co., Ltd.), JER1031S (manufactured by Japan Epoxy Resin Co., Ltd.) and the like.

  Specific examples of the polymer having an oxetanyl group in the side chain and the polymerizable monomer or oligomer having two or more oxetanyl groups in the molecule include Aronoxetane OXT-121, OXT-221, OX-SQ, PNOX ( As described above, Toagosei Co., Ltd.) can be used.

In the case of synthesizing by introducing into a polymer side chain, for example, the introduction reaction includes tertiary amines such as triethylamine and benzylmethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, pyridine, The reaction can be carried out in an organic solvent at a reaction temperature of 50 to 150 ° C. for several to several tens of hours using triphenylphosphine or the like as a catalyst. The introduction amount of the alicyclic epoxy unsaturated compound is preferably controlled so that the acid value of the obtained polymer is in a range satisfying 5 to 200 KOH · mg / g. Further, the molecular weight is preferably 500 to 5000000, more preferably 1000 to 500000 in terms of weight average.
As the epoxy unsaturated compound, those having a glycidyl group as an epoxy group such as glycidyl (meth) acrylate and allyl glycidyl ether can be used, but preferred are unsaturated compounds having an alicyclic epoxy group. Examples of such compounds include the following compounds.

  About these polymeric compounds, the details of usage methods, such as the structure, single use or combined use, and addition amount, can be arbitrarily set according to the final performance design of a near-infrared absorptive composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. In addition, from the viewpoint of increasing the strength of the near infrared cut filter, those having three or more functionalities are preferable. Further, different functional numbers / different polymerizable groups (for example, acrylic acid esters, methacrylic acid esters, styrene compounds, vinyl ether compounds). A method of adjusting both sensitivity and intensity by using a combination of these materials is also effective. In addition, selection and use of polymerizable compounds are important for compatibility and dispersibility with other components (eg, metal oxides, dyes, polymerization initiators) contained in the near-infrared absorbing composition. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a support.

The amount of the polymerizable compound added to the composition of the present invention is 1 to 80% by mass, more preferably 15 to 70% by mass, and particularly preferably 20 to 60% by mass with respect to the total solid content excluding the solvent. It is preferable to add.
Only one type of polymerizable compound or two or more types may be used, and in the case of two or more types, the total amount falls within the above range.

<Binder polymer>
In the present invention, a binder polymer can be further contained in addition to the polymerizable compound as necessary for the purpose of improving the film properties. As the binder polymer, an alkali-soluble resin is preferably used. By containing an alkali-soluble resin, there is an effect in improving heat resistance and fine adjustment of coating properness.

The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable. From the viewpoint of development control, acrylic resins and acrylamide resins are preferable. Resins and acrylic / acrylamide copolymer resins are preferred.
Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. The group is soluble in an organic solvent and developed with a weak alkaline aqueous solution. Possible are preferable, and (meth) acrylic acid is particularly preferable. These acid groups may be used alone or in combination of two or more.
Examples of the monomer capable of imparting an acid group after the polymerization include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate. These monomers for introducing an acid group may be only one type or two or more types. In order to introduce an acid group into an alkali-soluble binder, for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as “monomer for introducing an acid group”) .) May be polymerized as a monomer component. In addition, when introducing an acid group using a monomer capable of imparting an acid group after polymerization as a monomer component, for example, a treatment for imparting an acid group as described later is required after the polymerization.

  For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and experimental conditions are determined. It can also be done.

  As the linear organic polymer used as the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. , Maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenolic resins such as novolak resins, etc., acid cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to polymers having a hydroxyl group. Can be mentioned. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macro Examples of N-substituted maleimide monomers described in JP-A-10-300922 such as monomers and polymethylmethacrylate macromonomers include N-phenylmaleimide and N-cyclohexylmaleimide. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.

As an alkali-soluble resin, the following general formula (ED)
(In formula (ED), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.) It is also preferable that the polymer (a) obtained by polymerizing the monomer component essential to “ether dimer”) is contained as the essential polymer component (A). Thereby, the composition of this invention can form the cured coating film which was very excellent also in heat resistance and transparency. In the general formula (1) showing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited. Linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl An alkyl group substituted with an aryl group such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance.

  Specific examples of the ether dimer include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di Stearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2-ethylhexyl) -2 , 2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxyethyl) -2 , 2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis (methylene)] bis- 2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butylcyclohexyl) 2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tricyclodecanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 '-[oxybis (Methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, and the like. Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be only one kind or two or more kinds. The structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

  In this invention, it is preferable that the structural unit derived from an ether dimer is 1-50 mol% of the whole, and it is more preferable that it is 1-20 mol%.

Other monomers may be copolymerized with the ether dimer.
Other monomers that can be copolymerized with the ether dimer include, for example, a monomer for introducing an acid group, a monomer for introducing a radical polymerizable double bond, and an epoxy group. Monomers and other copolymerizable monomers other than these may be mentioned. Only 1 type may be used for such a monomer and it may use 2 or more types.

Examples of the monomer for introducing an acid group include monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid, monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide, maleic anhydride, and anhydride. And monomers having a carboxylic anhydride group such as itaconic acid. Among these, (meth) acrylic acid is particularly preferable.
The monomer for introducing an acid group may be a monomer that can give an acid group after polymerization, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, Examples thereof include a monomer having an epoxy group such as glycidyl (meth) acrylate, and a monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate. When using a monomer for introducing a radical polymerizable double bond, when using a monomer capable of imparting an acid group after polymerization, it is necessary to perform a treatment for imparting an acid group after polymerization. The treatment for adding an acid group after polymerization varies depending on the type of monomer, and examples thereof include the following treatment. In the case of using a monomer having a hydroxyl group, for example, a treatment of adding an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride or the like can be mentioned. In the case of using a monomer having an epoxy group, for example, a compound having an amino group and an acid group such as N-methylaminobenzoic acid or N-methylaminophenol is added, or, for example, (meth) acrylic For example, a treatment of adding an acid anhydride such as succinic acid anhydride, tetrahydrophthalic acid anhydride, maleic acid anhydride to the hydroxyl group generated after adding an acid such as an acid can be mentioned. In the case of using a monomer having an isocyanate group, for example, a treatment of adding a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid can be mentioned.

  When the polymer formed by polymerizing the monomer component containing the compound represented by the general formula (ED) contains a monomer for introducing an acid group, the content ratio is not particularly limited, In a monomer component, 5-70 mass% is preferable, More preferably, it is 10-60 mass%.

  Examples of the monomer for introducing a radical polymerizable double bond include, for example, monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride Monomers having a group; monomers having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether; . When using a monomer for introducing a radical polymerizable double bond, it is necessary to perform a treatment for imparting a radical polymerizable double bond after polymerization. The treatment for imparting a radical polymerizable double bond after polymerization differs depending on the type of monomer that can impart a radical polymerizable double bond to be used, and examples thereof include the following treatment. If a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid is used, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p- ) Treatment of adding a compound having an epoxy group such as vinylbenzyl glycidyl ether and a radically polymerizable double bond. In the case of using a monomer having a carboxylic anhydride group such as maleic anhydride or itaconic anhydride, a treatment for adding a compound having a hydroxyl group and a radical polymerizable double bond such as 2-hydroxyethyl (meth) acrylate Is mentioned. If a monomer having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzylglycidyl ether is used, (meth) The process which adds the compound which has acid groups, such as acrylic acid, and a radically polymerizable double bond is mentioned.

  When the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) contains a monomer for introducing a radical polymerizable double bond, the content ratio is particularly limited. Although not, 5-70 mass% is preferable in all the monomer components, More preferably, it is 10-60 mass%.

Examples of the monomer for introducing an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. Can be mentioned.
When the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) contains a monomer for introducing an epoxy group, the content ratio is not particularly limited, In a monomer component, 5-70 mass% is preferable, More preferably, it is 10-60 mass%.

  Examples of other copolymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylate n. -Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2- (meth) acrylic acid 2- (Meth) acrylic acid esters such as hydroxyethyl; aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; butadiene, isoprene and the like Butadiene or substituted butadiene compounds; ethylene, propylene, vinyl chloride Ethylene or substituted ethylene compound such as acrylonitrile, vinyl esters such as vinyl acetate; and the like. Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable in terms of good transparency and resistance to heat resistance.

  When the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) contains another copolymerizable monomer, the content ratio is not particularly limited, but is 95% by mass. The following is preferable, and it is more preferable that it is 85 mass% or less.

The weight average molecular weight of the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) is not particularly limited, but is formed by the viscosity of the colored radiation-sensitive composition and the composition. From the viewpoint of the heat resistance of the coating film, it is preferably 2000 to 200000, more preferably 5000 to 100000, and still more preferably 5000 to 20000.
Moreover, when the polymer formed by polymerizing the monomer component containing the compound represented by the general formula (ED) has an acid group, the acid value is preferably 30 to 500 mgKOH / g, more preferably 50. It should be ˜400 mg KOH / g.

A polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) can be easily obtained by polymerizing at least the above-mentioned monomer essentially containing an ether dimer. . At this time, the cyclization reaction of the ether dimer proceeds simultaneously with the polymerization to form a tetrahydropyran ring structure.
The polymerization method applied to the synthesis of the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) is not particularly limited, and various conventionally known polymerization methods can be adopted. However, it is particularly preferable to use a solution polymerization method. Specifically, for example, in accordance with the method for synthesizing the polymer (a) described in JP-A-204-300204, a polymer formed by polymerizing a monomer component containing a compound represented by the general formula (ED) Can combine

  Hereinafter, although the exemplary compound of the polymer formed by superposing | polymerizing the monomer component containing the compound represented by general formula (ED) is shown, this invention is not limited to these. The composition ratio of the exemplary compounds shown below is mol%.

In the present invention, in particular, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate (hereinafter referred to as “DM”), benzyl methacrylate (hereinafter referred to as “BzMA”), methyl methacrylate (hereinafter referred to as “MMA”). ), Methacrylic acid (hereinafter referred to as “MAA”), and glycidyl methacrylate (hereinafter referred to as “GMA”). In particular, the molar ratio of DM: BzMA: MMA: MAA: GMA is preferably 5-15: 40-50: 5-15: 5-15: 20-30. It is preferable that 95% by mass or more of the components constituting the copolymer used in the present invention is these components. Moreover, it is preferable that the weight average molecular weights of this polymer are 9000-20000.

In the present invention, an alkali-soluble phenol resin can also be preferably used. Examples of the alkali-soluble phenol resin include novolak resins and vinyl polymers.
Examples of the novolac resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of the phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, and bisphenol A.
Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, and benzaldehyde.
The said phenols and aldehydes can be used individually or in combination of 2 or more types.

  Specific examples of the novolak resin include, for example, a condensation product of metacresol, paracresol or a mixture thereof and formalin.

  The novolak resin may be adjusted in molecular weight distribution by means of fractionation or the like. Moreover, you may mix the low molecular weight component which has phenolic hydroxyl groups, such as bisphenol C and bisphenol A, with the said novolak resin.

  As the alkali-soluble resin, in particular, a benzyl (meth) acrylate / (meth) acrylic acid copolymer and a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are suitable. In addition, a copolymer of 2-hydroxyethyl methacrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2-hydroxy -3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / Benzyl methacrylate / methacrylic acid copolymer.

The acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and most preferably 70 to 120 mgKOH / g.
Further, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and most preferably 7,000 to 20,000.

  The content of the binder polymer in the present invention is preferably 1% by mass to 80% by mass, more preferably 10% by mass to 70% by mass, and more preferably 20% to 20% by mass with respect to the total solid content of the composition. More preferably, it is 60 mass%.

<Solvent>
It is preferable that the composition of this invention contains a solvent, and it is more preferable that a solvent is included in the ratio of 50-80 mass% with respect to a composition. Only one type of solvent may be used, or two or more types may be used, and in the case of two or more types, the total amount falls within the above range. The solvent is preferably contained in an amount of 50 to 75% by mass, more preferably 51 to 70% by mass, and particularly preferably 51 to 65% by mass with respect to the composition.
The solvent used in the present invention is not particularly limited, and can be appropriately selected depending on the purpose as long as it can uniformly dissolve or disperse each component of the composition of the present invention. For example, methanol, ethanol , Alcohols such as normal-propanol, isopropanol, normal-butanol, secondary butanol, normal-hexanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, cyclohexanone, cyclopentanone; ethyl acetate, butyl acetate Esters such as methyl acetate, normal-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, propylene glycol monomethyl ether acetate, and methoxypropyl acetate; Aromatic hydrocarbons such as ethylene, benzene and ethylbenzene; halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride and monochlorobenzene; tetrahydrofuran, diethyl ether, ethylene glycol monomethyl Ethers such as ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol, propylene glycol monomethyl ether; dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane and the like. These may be used alone or in combination of two or more.

<Polymerization initiator>
The composition of the present invention may contain a polymerization initiator. Only one type of polymerization initiator may be used, or two or more types may be used, and in the case of two or more types, the total amount falls within the above range. 0.01 mass%-30 mass% are preferable, 0.1 mass%-20 mass% are more preferable, 0.1 mass%-15 mass% are especially preferable.
The polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound by light or heat, or both, and can be appropriately selected according to the purpose. It is preferable that When polymerization is initiated by light, those having photosensitivity to visible light from the ultraviolet region are preferred.
Moreover, when starting superposition | polymerization with a heat | fever, the initiator decomposed | disassembled at 150 to 250 degreeC is preferable.

The polymerization initiator that can be used in the present invention is preferably a compound having at least an aromatic group, such as an acylphosphine compound, an acetophenone compound, an α-aminoketone compound, a benzophenone compound, a benzoin ether compound, and a ketal derivative. Compounds, thioxanthone compounds, oxime compounds, hexaarylbiimidazole compounds, trihalomethyl compounds, azo compounds, organic peroxides, diazonium compounds, iodonium compounds, sulfonium compounds, azinium compounds, benzoin ether compounds, ketal derivative compounds, metallocene compounds, etc. Onium salt compounds, organoboron salt compounds, disulfone compounds, and the like.
From the viewpoint of sensitivity, oxime compounds, acetophenone compounds, α-aminoketone compounds, trihalomethyl compounds, hexaarylbiimidazole compounds, and thiol compounds are preferred.
Examples of the polymerization initiator suitable for the present invention will be given below, but the present invention is not limited thereto.

  Specific examples of the acetophenone compound include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and p-dimethylaminoacetophenone. 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-methyl -1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl 2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] Examples include -1-butanone and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one.

  As the trihalomethyl compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6-tris (Monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (Trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) ) -S-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) ) -S-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6- Bis (tribromomethyl) -s-triazine and the like can be mentioned.

  As the hexaarylbiimidazole compound, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, 4,622,286, etc. And, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) )) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5 '-Tetraphenylbi Dazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

Examples of oxime compounds include J.M. C. S. Perkin II (1979) 1653-1660, J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, Journal of Applied Polymer Science (2012) pp. 725-731, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, IRGACURE OXE 01 (1.2-octanedione, 1 manufactured by BASF Japan Ltd.) -[4- (phenylthio)-, 2- (O-benzoyloxime)]), IRGACURE OXE 02 (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O-acetyloxime)), 2- (acetyloxyiminomethyl) thioxanthen-9-one and the like.
Preferably, it can also be suitably used for the cyclic oxime compounds described in JP2007-231000A and JP2007-322744A.
Other preferable examples include an oxime compound having a specific substituent described in JP-A-2007-269977 and an oxime compound having a thioaryl group described in JP-A-2009-191061.
Specifically, as the oxime compound, a compound represented by the following formula (1) is also preferable. The N—O bond of the oxime may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

(In formula (1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.)
The monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group. Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group. , Dodecyl group, okdadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1- Naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2- Methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, and , 3 Nitorofenashiru group can be exemplified.

  The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, specifically, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, or a 9-anthryl group. 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m- and p-tolyl group, Xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, tarnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, ASEAN Trirenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, ter Nthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, specifically, an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2 -Methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, and And 4-methoxybenzoyl group.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, specifically, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, or a hexyloxy group. Examples thereof include a carbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

  Specific examples of the aryloxycarbonyl group which may have a substituent include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanyl. Phenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxy Carbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl , 4-fluorophenyl oxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and a 4-methoxy phenyloxy carbonyl group can be exemplified.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.
Specifically, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiyl Nyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl Group Midinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolidinyl group Examples include a group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, and thioxanthryl group.

  Specific examples of the alkylthiocarbonyl group which may have a substituent include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, and an octadecylthiocarbonyl group. Examples thereof include a group and a trifluoromethylthiocarbonyl group.

  Specific examples of the arylthiocarbonyl group which may have a substituent include a 1-naphthylthiocarbonyl group, a 2-naphthylthiocarbonyl group, a 4-methylsulfanylphenylthiocarbonyl group, and a 4-phenylsulfanylphenylthiocarbonyl group. 4-dimethylaminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3 -Chlorophenylthiocarbonyl group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenyl Two thiocarbonyl group, and a and a 4-methoxyphenylthiocarbonyl group.

  The monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Among them, the structure shown below is particularly preferable.
In the following structure, Y, X, and n have the same meanings as Y, X, and n in formula (2) described later, and preferred examples are also the same.

Examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cyclohexylene group, and an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among them, A is an alkylene substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating. Group, alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) An alkylene group substituted with

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent. Examples of the substituent include the same substituents as those introduced into the substituted aryl group mentioned above as specific examples of the aryl group which may have a substituent.
Of these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  In the formula (1), it is preferable in terms of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure. Me represents a methyl group, and Et represents an ethyl group.

  The oxime compound is also preferably a compound represented by the following formula (2).

(In formula (2), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents 0-5. (It is an integer.)
R, A, and Ar in formula (2) have the same meanings as R, A, and Ar in formula (1), and preferred examples are also the same.

  Examples of the monovalent substituent represented by X include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, a heterocyclic group, and a halogen atom. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Among these, X is preferably an alkyl group from the viewpoints of solvent solubility and improvement in absorption efficiency in the long wavelength region.
Moreover, n in Formula (2) represents the integer of 0-5, and the integer of 0-2 is preferable.

  Examples of the divalent organic group represented by Y include the structures shown below. In the group shown below, * represents the bonding position between Y and the adjacent carbon atom in the formula (2).

  Among these, from the viewpoint of increasing sensitivity, the following structures are preferable.

  Furthermore, the oxime compound is also preferably a compound represented by the following formula (3).

  R, X, A, Ar, and n in Formula (3) have the same meanings as R, X, A, Ar, and n in Formula (2), respectively, and preferred examples are also the same.

  Specific examples (PIox-1) to (PIox-13) of oxime compounds that can be suitably used are shown below, but the present invention is not limited thereto.

  The oxime compound preferably has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and has a high absorbance at 365 nm and 455 nm. Particularly preferred.

From the viewpoint of sensitivity, the oxime compound preferably has a molar extinction coefficient at 365 nm or 405 nm of 3,000 to 300,000, more preferably 5,000 to 300,000, and 10,000 to 200. Is particularly preferred.
For the molar extinction coefficient of the compound, a known method can be used. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Vary Inc., Carry-5 spectrphotometer) using an ethyl acetate solvent is used. It is preferable to measure at a concentration of / L.

The photopolymerization initiator is more preferably a compound selected from the group consisting of oxime compounds, acetophenone compounds, and acylphosphine compounds. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969, an acylphosphine oxide initiator described in Japanese Patent No. 4225898, and the oxime initiator described above, As the oxime initiator, compounds described in JP-A No. 2001-233842 can also be used.
As the acetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Japan Ltd.) can be used. As the acylphosphine initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF Japan Ltd.) can be used.

<Surfactant>
The composition of the present invention may contain a surfactant. Only one type of surfactant may be used, or two or more types may be combined. The addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass and more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the composition of the present invention. More preferably, it is 0.01 to 0.1% by mass or less.
As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

In particular, since the composition of the present invention contains a fluorosurfactant, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved. Sex can be improved more.
That is, when a film is formed using a coating liquid to which a composition containing a fluorosurfactant is applied, the wettability to the coated surface is reduced by reducing the interfacial tension between the coated surface and the coating liquid. Is improved, and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

  The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in near-infrared absorbing compositions. .

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA), and the like.

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sol Perth 20000 (manufactured by Nippon Lubrizol Corporation), and the like.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

  Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

  Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. “Silicone SH29PA”, “Toresilicone SH30PA”, “Toresilicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF” manufactured by Momentive Performance Materials, Inc. -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by Big Chemie.

<Other ingredients>
In the near-infrared absorbing composition of the present invention, in addition to the essential components and the preferred additives, other components may be appropriately selected according to the purpose as long as the effects of the present invention are not impaired.
Examples of other components that can be used in combination include a binder polymer, a dispersant, a sensitizer, a crosslinking agent, a curing accelerator, a filler, a thermosetting accelerator, a thermal polymerization inhibitor, and a plasticizer. Surface adhesion promoters and other auxiliaries (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling promoters, antioxidants, fragrances, surface tension modifiers, chain transfer agents Etc.) may be used in combination.
By appropriately containing these components, properties such as stability and film physical properties of the target near-infrared absorption filter can be adjusted.
These components include, for example, paragraph number 0183 of JP2012-003225A, paragraph number 0101-0102 of JP2008-250074, paragraph number 0103-0104 of JP2008-250074, The description of paragraph numbers 0107 to 0109 of 2008-250074 can be referred to, and the contents thereof are incorporated in the present specification.

  The near-infrared absorptive composition of the present invention can be made into a liquid, for example, a near-infrared cut filter can be easily manufactured by a simple process of forming a film by applying a pin. Insufficient production suitability in the near-infrared cut filter can be improved.

Although the use of the near-infrared absorptive composition of this invention is not specifically limited, For the near-infrared cut filter in the light-receiving side of a solid-state image sensor board | substrate (For example, for the near-infrared cut filter with respect to a wafer level lens), a solid-state image sensor board | substrate For the near infrared cut filter on the back surface side (the side opposite to the light receiving side), and the like, and preferably for the light shielding film on the light receiving side of the solid-state imaging device substrate. In particular, the present invention is preferably used by forming a coating film on an image sensor for a solid-state imaging device.
Further, the viscosity of the near-infrared absorbing composition of the present invention is preferably in the range of 1 mPa · s to 3000 mPa · s, more preferably in the range of 10 mPa · s to 2000 mPa · s, and further preferably. Is in the range of 100 mPa · s to 1500 mPa · s.
When the near-infrared absorbing composition of the present invention is for a near-infrared cut filter on the light-receiving side of a solid-state imaging device substrate, a range of 10 mPa · s or more and 3000 mPa · s or less from the viewpoint of thick film formation and uniform coating properties. More preferably, it is in the range of 500 mPa · s to 1500 mPa · s, and most preferably in the range of 700 mPa · s to 1400 mPa · s.

The present invention also relates to a near-infrared cut filter obtained using the above-described near-infrared absorbing composition of the present invention. Since such a near-infrared cut filter is formed from the near-infrared absorbing composition of the present invention, it has a high light-shielding property (near-infrared shielding property) in the near-infrared region, and translucency (visible) in the visible-light region. It is a near-infrared cut filter having high light transmission) and excellent weather resistance such as light resistance and moisture resistance. In particular, the present invention is useful as a near-infrared cut filter having a wavelength region of 700 to 2500 nm.
Furthermore, the present invention provides a near-infrared cut filter having a step of forming a film by applying (preferably spin-coating) the near-infrared absorbing composition of the present invention on the light-receiving side of the solid-state imaging device substrate. Also related to the method.

  In order to form a near-infrared cut filter, first, a film is formed from the near-infrared absorbing composition of the present invention. If a film | membrane is a film | membrane formed including the said near-infrared absorptive composition, there will be no restriction | limiting in particular, About a film thickness, a laminated structure, etc., it can select suitably according to the objective.

  As the method for forming the film, the near-infrared absorbing composition of the present invention (coating solution in which the solid content in the composition is dissolved, emulsified or dispersed) is directly applied on the support (preferably coated). And a method of forming by drying.

The support is provided on the light receiving side of the solid-state imaging device substrate, whether it is a solid-state imaging device substrate or another substrate (for example, a glass substrate 30 described later) provided on the light-receiving side of the solid-state imaging device substrate. A layer such as a flattening layer may also be used.
The method of applying the near-infrared absorbing composition (coating liquid) on the support can be carried out by using, for example, a spin coater, a slit spin coater or the like.
In addition, the drying conditions of the coating film vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 seconds to 150 ° C. for about 30 seconds to 15 minutes.

  There is no restriction | limiting in particular as thickness of the said film | membrane, Although it can select suitably according to the objective, For example, 1 micrometer-100 micrometers are preferable, 1 micrometer-50 micrometers are more preferable, 1.0 micrometer-4.0 micrometers are especially preferable.

  The method for forming a near-infrared cut filter using the near-infrared absorbing composition of the present invention may include other steps.

  There is no restriction | limiting in particular as said other process, According to the objective, it can select suitably, For example, the surface treatment process of a base material, a preheating process (prebaking process), a hardening process process, a post-heating process (post-baking) Process).

<Pre-heating process / Post-heating process>
The heating temperature in the preheating step and the postheating step is usually 80 ° C to 200 ° C, and preferably 90 ° C to 150 ° C.
The heating time in the preheating step and the postheating step is usually 30 seconds to 240 seconds, and preferably 60 seconds to 180 seconds.

<Curing process>
The curing process is a process of curing the formed film as necessary, and the mechanical strength of the near-infrared cut filter is improved by performing this process.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably. Here, in the present invention, “exposure” is used to include not only light of various wavelengths but also irradiation of radiation such as electron beams and X-rays.
The exposure is preferably performed by irradiation of radiation, and as the radiation that can be used for the exposure, ultraviolet rays such as electron beams, KrF, ArF, g rays, h rays, i rays and visible light are particularly preferably used. Preferably, KrF, g line, h line, and i line are preferable.
As an exposure method. Examples include stepper exposure and exposure with a high-pressure mercury lamp.
Exposure is more preferably 5mJ / cm ² ~3000mJ / cm ² is preferably ^{10mJ / cm 2 ~2000mJ / cm 2} , 50mJ / cm 2 ~1000mJ / cm 2 being most preferred.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the formed film. When the near-infrared absorbing composition contains a polymerizable compound, the entire surface exposure promotes curing of the polymerization component in the film formed from the composition, further curing of the film, mechanical strength, Durability is improved.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

Moreover, as a method of the whole surface heat treatment, a method of heating the entire surface of the formed film can be mentioned. By heating the entire surface, the film strength of the pattern is increased.
120 to 250 degreeC is preferable and the heating temperature in a whole surface heating has more preferable 120 to 250 degreeC. When the heating temperature is 120 ° C. or higher, the film strength is improved by heat treatment, and when the heating temperature is 250 ° C. or lower, the components in the film are decomposed and the film quality is prevented from becoming weak and brittle.
The heating time in the entire surface heating is preferably 3 minutes to 180 minutes, and more preferably 5 minutes to 120 minutes.
There is no restriction | limiting in particular as an apparatus which performs whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

  Moreover, this invention is a camera module which has a solid-state image sensor board | substrate and the near-infrared cut filter arrange | positioned at the light-receiving side of the said solid-state image sensor board | substrate, Comprising: The said near-infrared cut filter is a near-infrared cut filter of this invention. It also relates to the camera module.

Hereinafter, although the camera module which concerns on embodiment of this invention is demonstrated, referring FIG.1 and FIG.2, this invention is not limited by the following specific examples.
Throughout FIGS. 1 and 2, common portions are denoted by common reference numerals.
In the description, “upper”, “upper”, and “upper” refer to the side far from the silicon substrate 10, and “lower”, “lower”, and “lower” are the sides closer to the silicon substrate 10. Point to.

FIG. 1 is a schematic cross-sectional view illustrating a configuration of a camera module including a solid-state imaging device.
A camera module 200 shown in FIG. 1 is connected to a circuit board 70 that is a mounting board via solder balls 60 that are connection members.
Specifically, the camera module 200 is provided on the first main surface side (light receiving side) of the solid-state image sensor substrate 100 and the solid-state image sensor substrate 100 provided with an image sensor section on the first main surface of the silicon substrate. The flattening layer 46 (not shown in FIG. 1), the near-infrared cut filter 42 provided on the flattening layer 46, and the glass substrate 30 (light transmitting property) disposed above the near-infrared cut filter 42 A substrate), a lens holder 50 having an imaging lens 40 disposed in an internal space above the glass substrate 30, a light shielding and electromagnetic shield 44 disposed so as to surround the solid-state imaging device substrate 100 and the glass substrate 30, It is configured with. Each member is bonded by an adhesive 20 (not shown in FIG. 1) and 45.
The present invention is a method of manufacturing a camera module having a solid-state image pickup device substrate and a near-infrared cut filter disposed on the light-receiving side of the solid-state image pickup device substrate. The present invention also relates to a step of forming a film by applying the near infrared absorbing composition.
Therefore, in the camera module according to the present embodiment, for example, the near-infrared cut filter 42 is formed by forming a film by applying the near-infrared absorbing composition of the present invention on the planarizing layer 46. . The method for producing a near-infrared cut filter by forming a film by coating is as described above.
In the camera module 200, the incident light hν from the outside passes through the imaging lens 40, the glass substrate 30, the near-infrared cut filter 42, and the planarization layer 46 in order, and then reaches the imaging device portion of the solid-state imaging device substrate 100. It has become.
The camera module 200 is connected to the circuit board 70 via a solder ball 60 (connection material) on the second main surface side of the solid-state imaging device substrate 100.

FIG. 2 is an enlarged cross-sectional view of the solid-state imaging device substrate 100 in FIG.
The solid-state image sensor substrate 100 includes a silicon substrate 10 as a base, an image sensor 12, an interlayer insulating film 13, a base layer 14, a red color filter 15R, a green color filter 15G, a blue color filter 15B, an overcoat 16, a micro The lens 17, the light shielding film 18, the insulating film 22, the metal electrode 23, the solder resist layer 24, the internal electrode 26, and the element surface electrode 27 are configured.
However, the solder resist layer 24 may be omitted.

First, the configuration on the first main surface side of the solid-state imaging device substrate 100 will be mainly described.
As shown in FIG. 2, an imaging element unit in which a plurality of imaging elements 12 such as CCDs and CMOSs are two-dimensionally arranged is provided on the first main surface side of the silicon substrate 10 that is a base of the solid-state imaging element substrate 100. ing.
An interlayer insulating film 13 is formed on the image sensor 12 in the image sensor section, and a base layer 14 is formed on the interlayer insulating film 13. Furthermore, on the base layer 14, a red color filter 15 R, a green color filter 15 G, and a blue color filter 15 B (hereinafter collectively referred to as “color filter 15”) corresponding to the image sensor 12. ) Are arranged.
A light shielding film (not shown) may be provided around the boundary between the red color filter 15R, the green color filter 15G, and the blue color filter 15B, and the periphery of the imaging element unit. This light shielding film can be produced using, for example, a known black color resist.
An overcoat 16 is formed on the color filter 15, and a microlens 17 is formed on the overcoat 16 so as to correspond to the imaging element 12 (color filter 15).
The planarizing layer 46 is provided on the microlens 17.

In addition, a peripheral circuit (not shown) and an internal electrode 26 are provided in the periphery of the image sensor section on the first main surface side, and the internal electrode 26 is electrically connected to the image sensor 12 via the peripheral circuit. Has been.
Furthermore, an element surface electrode 27 is formed on the internal electrode 26 with the interlayer insulating film 13 interposed therebetween. In the interlayer insulating film 13 between the internal electrode 26 and the element surface electrode 27, a contact plug (not shown) for electrically connecting these electrodes is formed. The element surface electrode 27 is used for applying a voltage and reading a signal through the contact plug and the internal electrode 26.
A base layer 14 is formed on the element surface electrode 27. An overcoat 16 is formed on the base layer 14. The base layer 14 and the overcoat 16 formed on the element surface electrode 27 are opened to form a pad opening, and a part of the element surface electrode 27 is exposed.

The above is the configuration of the first main surface side of the solid-state imaging device substrate 100. Instead of providing the near-infrared cut filter 42 on the flattening layer 46, between the base layer 14 and the color filter 15, or A form in which a near-infrared cut filter is provided between the color filter 15 and the overcoat 16 may be employed.
On the first main surface side of the solid-state image sensor substrate 100, an adhesive 20 is provided around the image sensor section, and the solid-state image sensor substrate 100 and the glass substrate 30 are bonded via the adhesive 20.

  The silicon substrate 10 has a through hole that penetrates the silicon substrate 10, and a through electrode that is a part of the metal electrode 23 is provided in the through hole. The imaging element portion and the circuit board 70 are electrically connected by the through electrode.

Next, the configuration on the second main surface side of the solid-state imaging device substrate 100 will be mainly described.
On the second main surface side, an insulating film 22 is formed from the second main surface to the inner wall of the through hole.
On the insulating film 22, a metal electrode 23 patterned so as to extend from a region on the second main surface of the silicon substrate 10 to the inside of the through hole is provided. The metal electrode 23 is an electrode for connecting the image pickup element portion in the solid-state image pickup element substrate 100 and the circuit board 70.
The through electrode is a portion of the metal electrode 23 formed inside the through hole. The through electrode penetrates part of the silicon substrate 10 and the interlayer insulating film, reaches the lower side of the internal electrode 26, and is electrically connected to the internal electrode 26.

Further, a solder resist layer 24 (protective layer) is provided on the second main surface side, which covers the second main surface on which the metal electrode 23 is formed and has an opening that exposes a portion on the metal electrode 23. Insulating film).
Further, on the second main surface side, there is provided a light shielding film 18 that covers the second main surface on which the solder resist layer 24 is formed and has an opening through which a part of the metal electrode 23 is exposed. It has been.
In FIG. 2, the light shielding film 18 is patterned so as to cover a part of the metal electrode 23 and expose the remaining part, but may be patterned so as to expose the entire metal electrode 23. (The same applies to the patterning of the solder resist layer 24).
The solder resist layer 24 may be omitted, and the light shielding film 18 may be directly formed on the second main surface on which the metal electrode 23 is formed.

  A solder ball 60 as a connection member is provided on the exposed metal electrode 23, and the metal electrode 23 of the solid-state imaging device substrate 100 and a connection electrode (not shown) of the circuit board 70 are connected via the solder ball 60. , Are electrically connected.

As mentioned above, although the structure of the solid-state image sensor substrate 100 was demonstrated, the method as described in Paragraph 0033-0068 of Unexamined-Japanese-Patent No. 2009-158863, the method as described in Paragraph 0036-0065 of Unexamined-Japanese-Patent No. 2009-99951, etc. It can be formed by a known method.
The interlayer insulating film 13 is formed as a SiO ₂ film or a SiN film, for example, by sputtering, CVD (Chemical Vapor Deposition), or the like.
The color filter 15 is formed by photolithography using a known color resist, for example.
The overcoat 16 and the base layer 14 are formed, for example, by photolithography using a known organic interlayer film forming resist.
The microlens 17 is formed by photolithography or the like using, for example, a styrene polymer.
The solder resist layer 24 is preferably formed by photolithography using a known solder resist containing, for example, a phenolic polymer, a polyimide polymer, or an amine polymer.
The solder ball 60 is formed using, for example, Sn—Ag, Sn—Cu, Sn—Ag—Cu as Sn—Pb (eutectic), 95Pb—Sn (high lead high melting point solder), and Pb free solder. . The solder ball 60 is formed in a spherical shape having a diameter of 100 μm to 1000 μm (preferably a diameter of 150 μm to 700 μm), for example.
The internal electrode 26 and the element surface electrode 27 are formed as a metal electrode such as Cu by CMP (Chemical Mechanical Polishing) or photolithography and etching, for example.
The metal electrode 23 is formed as a metal electrode such as Cu, Au, Al, Ni, W, Pt, Mo, Cu compound, W compound, and Mo compound by sputtering, photolithography, etching, and electrolytic plating, for example. The metal electrode 23 may have a single layer configuration or a stacked configuration including two or more layers. The film thickness of the metal electrode 23 is, for example, 0.1 μm to 20 μm (preferably 0.1 μm to 10 μm). The silicon substrate 10 is not particularly limited, but a silicon substrate that is thinned by scraping the back surface of the substrate can be used. Although the thickness of the substrate is not limited, for example, a silicon wafer having a thickness of 20 μm to 200 μm (preferably 30 to 150 μm) is used.
The through hole of the silicon substrate 10 is formed by, for example, photolithography and RIE (Reactive Ion Etching).

  As mentioned above, although one Embodiment of the camera module was described with reference to FIG.1 and FIG.2, the said one embodiment is not restricted to the form of FIG.1 and FIG.2.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

Example 1
<Method for preparing phosphate copper complex>
Copper benzoate (manufactured by Kanto Chemical Co., 3.6 g) was added to a solution obtained by adding a 1: 1 (mass ratio) mixture of exemplified compounds PE-47 and PE-48 (Johoku Chemical JPPA-514M) to 23 g of acetone. did. The amount of the phosphoric ester compound is 0.5 mol, 1 mol, 1.5 mol, 2 mol, 2.5 mol, 3 mol, 4 mol, 6 mol, 8 mol, 10 mol per 1 mol of copper benzoate. It mix | blended so that it might become a mole (it is set as reaction liquid 1-10 in order). After stirring for 3 hours, oil-like compounds 1 to 10 were obtained by performing hexane reprecipitation twice.

<Method for preparing spectral solution>
0.5 g of each of the reaction liquids 1 to 10 obtained above was collected and diluted with 20 ml of tetrahydrofuran (THF) (solutions 1 to 10). In addition, 0.2 g of the oily compound obtained above was diluted with 20 mL of THF (solid 1 to 10).

<Measurement of transmittance>
Using the solutions 1 to 10, transmittances at wavelengths of 500 nm and 800 nm were measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation).
The transmittance at 500 nm was evaluated as follows.
A: 80% or more B: 50% or more and less than 80% C: less than 50% The transmittance at 500 nm was evaluated as follows.
A: Less than 10% B: 10% or more and less than 20% C: 20% or more

<Measurement of maximum absorption wavelength>
Using the solutions 1 to 10, the maximum absorption wavelength was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation).
A: 800 nm or more B: 790 nm or more and less than 800 nm C: less than 790 nm

(Example 2)
The mixture of phosphate ester compounds is a mixture of Exemplified compounds PE-58 and PE-59 (manufacturer: Unichemical Co., Ltd., product number: Phosmer PE), and the amount of phosphate ester compound is 1 mol of copper benzoate, A phosphate ester copper complex was prepared in the same manner as in Example 1 except that the amounts were 4 mol and 6 mol, respectively, and the transmittance and the maximum absorption wavelength were evaluated. The results are shown in the table below.

(Example 3)
The mixture of phosphate ester compounds is a mixture of Exemplified compounds PE-60 and PE-61 (manufacturer: Unichemical Co., Ltd., product number: Phosmer PP), and the amount of phosphate ester compound is 1 mol of copper benzoate, A phosphate ester copper complex was prepared in the same manner as in Example 1 except that the amounts were 4 mol and 6 mol, respectively, and the transmittance and the maximum absorption wavelength were evaluated. The results are shown in the table below.

In the said table | surface, the equivalent has shown as the ratio with respect to 1 mol of copper salts the quantity of the phosphate ester compound made to react with copper salt.
As is apparent from the above table, when 2 moles or more of a phosphate ester compound is reacted with 1 mole of copper salt, the transmittance at a wavelength of 500 nm is high, the transmittance at a wavelength of 800 nm is low, and the maximum is 790 nm or more. A composition having an absorption wavelength was obtained.

Example 4
In Examples 1 to 3, except that copper benzoate was changed to copper methacrylate or copper acrylate, respectively, and the amount of the phosphate ester compound was 6 mol per 1 mol of copper salt. Prepared a phosphate ester copper complex in the same manner as in Example 1, and evaluated the transmittance and the maximum absorption wavelength. The results are shown in the table below.

FIG. 3 shows the absorbance at each wavelength when the solutions 4 and 7 to 10 are used. Although five waveforms are described, when the molar ratio of phosphate compound / copper is 2/1, 4/1, 6/1, 8/1, 10/1 in descending order of absorbance at around 680 nm The waveform is shown. As is clear from FIG. 3, the maximum absorption wavelength is shifted to the longer wavelength side in the case of 4/1 to 10/1 as compared with the case where the molar ratio of the phosphate ester compound / copper is 2/1. I understand.
FIG. 4 shows the absorbance at each wavelength when the solids 4 and 7 are used. Although five waveforms are described, the waveforms when the molar ratio of the phosphate ester compound / copper is 2/1, 4/1 are shown in descending order of absorbance at 700 nm. As is apparent from the figure, the maximum absorption wavelength is shifted to the longer wavelength side in the case of 4/1 as compared with the case where the molar ratio of the phosphate ester compound / copper is 2/1.

Claims (13)

  The near-infrared absorptive composition containing the phosphate ester copper complex obtained by making more than 2 mol react a phosphate ester compound with respect to 1 mol of copper salts.   The maximum absorption wavelength is shifted to a longer wavelength side than the phosphate ester copper complex obtained by reacting 2 mol of the phosphate ester compound with respect to 1 mol of copper. The near-infrared absorptive composition of 1.   Furthermore, the near-infrared absorptive composition of Claim 1 or 2 containing the compound and solvent which have a polymeric group. The near-infrared absorptive composition of any one of Claims 1-3 in which the said phosphate ester compound is formed using the compound represented by following formula (1).
Formula (1)
_{(HO) n -P (= O} ) - (OR 2 Q) 3-n
(In the formula, Q represents a hydrogen atom or a polymerizable group, R ² represents a divalent linking group, and n represents 1 or 2.)   The near-infrared absorptive composition of Claim 4 whose said phosphate ester compound is a mixture of the compound of n in Formula (1), and the compound of n being 2.   The near-infrared absorptive composition of any one of Claims 1-5 whose maximum absorption wavelength of the said phosphate ester copper complex is 800 nm or more.   The near-infrared cut filter produced using the near-infrared absorptive composition in any one of Claims 1-6.   The manufacturing method of the near-infrared cut filter which has the process of forming a film | membrane by apply | coating the near-infrared absorptive composition of any one of Claims 1-6 in the light-receiving side of a solid-state image sensor board | substrate.   A near-infrared cut filter according to claim 7, or a near-infrared cut filter according to claim 8, which is disposed on a light-receiving side of the solid-state image sensor substrate and the solid-state image sensor substrate. A camera module having an infrared cut filter.   It is a manufacturing method of the camera module which has a solid-state image sensor board | substrate and the near-infrared cut filter arrange | positioned at the light-receiving side of the said solid-state image sensor board | substrate, Comprising: In the light-receiving side of a solid-state image sensor board | substrate, A method for producing a camera module, comprising a step of forming a film by applying the near-infrared absorbing composition according to claim 1.   The manufacturing method of the camera module of Claim 10 including light-irradiating and hardening | curing the film | membrane formed by apply | coating the said near-infrared absorptive composition.   A phosphate ester copper complex obtained by reacting more than 2 mol of a phosphate ester compound with respect to 1 mol of a copper salt.   The manufacturing method of a phosphate ester copper complex including making a phosphate ester compound react more than 2 mol with respect to 1 mol of copper salts.