TW201408673A - Near-infrared absorbing agent, near-infrared absorbing composition, near-infrared cut filter using the same, camera module, and manufacturing method thereof - Google Patents

Abstract

The present invention provides a copper phosphate complex which increases the gram absorption coefficient. The near-infrared ray absorbing agent of the present invention contains a copper phosphate complex which is obtained by reacting a compound having a range of O=P-O of from 104 to 120 degrees as a phosphate compound with a copper salt.

Description

Near-infrared absorbing agent, near-infrared absorbing composition, near-infrared cut filter using the same, camera module, and manufacturing method thereof

The present invention relates to a near infrared ray absorbing agent and a method of manufacturing the same. Further, the present invention relates to a near-infrared absorbing composition containing a near-infrared ray absorbing agent and a method for producing the same. Further, the present invention relates to a near-infrared cut filter using a near-infrared absorbing agent and a near-infrared absorbing composition, a method of manufacturing the same, and an image pickup module and a method of manufacturing the same.

In recent years, in a video camera, a digital still camera, a mobile phone with a camera function, etc., a charge coupled device (Charge-Coupled Device, CCD) which is a solid-state imaging element of a color image has been used. Or Complementary Metal-Oxide-Semiconductor (CMOS) image sensors, which use a light-emitting diode that is sensitive to near-infrared rays in the light-receiving portion thereof (silicon) Photodiode), it is necessary to perform visual sensitivity correction, and in most cases, a near-infrared cut filter is used.

As a material for forming such a near-infrared cut filter, a near-infrared absorbing composition is known (Japanese Patent Laid-Open No. Hei 11-052127, No. WO00/26952).

Further, in Journal of Applied Polymer Science, Vol. 67, 903-912 (1998), there is disclosed a method of forming a copper complex and polymerizing the copper complex to form a layer.

Here, in the case of preparing a near-infrared absorbing composition which can be formed into a layer by coating, it is required to have a high gram absorption coefficient as an index. The reason for this is that it is difficult to produce a film having a thick film thickness when forming a film of a near-infrared cut filter; if the gram absorption coefficient is high, the content of the copper complex can be reduced, and the film thickness can be made thin. However, in the above-mentioned Japanese Patent Laid-Open No. Hei 11-052127, No. WO00/26952, no research has been conducted on the gram absorption coefficient. In addition, in Journal of Applied Polymer Science, Vol. 67, 903-912 (1998), the following studies have not been conducted, that is, which factors have a large effect on the gram extinction coefficient, for example, regarding, for example, phosphodiester Study of the ligand structure of the O=PO angle-like complex of the compound. SUMMARY OF THE INVENTION An object of the present invention is to solve an aspect which has not been studied in the prior art, and an object thereof is to provide a near-infrared ray absorbing agent having a high gram absorption coefficient.

The inventors of the present invention conducted diligent research based on the above circumstances, and as a result, found that the gram extinction coefficient can be improved by reducing the O=P-O angle of the phosphodiester compound.

In general, the copper complex can basically adopt an octahedral complex structure, but by setting the O=P-O angle of the phosphodiester compound to a predetermined range, there is a tendency that the center of symmetry disappears. As a result, it was considered that the Laporte Forbidden was relieved, and the absorbance became strong, and as a result, the gram absorption coefficient increased.

Specifically, the above problem is solved by the following means <1>, preferably means <2>~ means <12>.

<1> A near-infrared ray absorbing agent containing a copper phosphate complex which is obtained by reacting a phosphodiester compound represented by the following formula with a copper salt.

(In the above formula, R is an organic group; and O = P-O angle is in the range of from 104 to 120 degrees).

<2> The near-infrared ray absorbing agent according to <1>, wherein the phosphodiester compound has an O=P-O angle of 110 degrees or less.

<3> The near-infrared ray absorbing agent according to <1> or <2>, wherein the phosphodiester compound has an O-P-O angle of from 104 to 109.5 degrees.

The near-infrared ray absorbing agent according to any one of <1> to <3> wherein the chrome absorption coefficient of the copper phosphate complex is 0.03 g/ml or more, wherein the gram absorption coefficient is absorbance/concentration. (The concentration refers to the weight (g) per 1 mL).

The near-infrared ray absorbing agent according to any one of <1> to <4> wherein the maximum absorption wavelength of the copper phosphate complex is 790 nm to 850 nm.

(6) A near-infrared absorbing composition containing a near-infrared ray absorbing agent, a polymerizable compound, and a solvent according to any one of <1> to <5>, and a phosphate ester in a near-infrared absorbing composition. The concentration of the copper complex is from 10% by mass to 80% by mass.

<7> The near-infrared absorbing composition according to <6>, wherein the compounding amount of the copper phosphate complex is 50% by mass to 99% by mass based on the total solid content of the near-infrared absorbing composition.

<8> The near-infrared absorbing composition according to <6> or <7>, which is used for forming a coating film on an image sensor for a solid-state image sensor.

<9> a near-infrared ray-cut filter according to any one of <1> to <5>, wherein the near-infrared ray according to any one of <6> to <8> or the near-infrared ray according to any one of <6> to <8>. Manufactured from an absorbent composition.

<10> A camera module having a solid-state image sensor substrate and a near-infrared cut filter as described in <9> disposed on a light receiving side of the solid-state image sensor substrate.

<11> A method of manufacturing an image pickup module, comprising: a solid-state image sensor substrate; and a method of manufacturing an image pickup module disposed on a light-receiving side near-infrared cut filter of the solid-state image sensor substrate, and the image pickup module The manufacturing method includes the step of forming a film by applying the near-infrared absorbing composition according to any one of <6> to <8> on the light-receiving side of the solid-state image sensor substrate.

<12> The method for producing an image pickup module according to the above aspect, comprising: curing a film formed by applying the near-infrared absorbing composition by light irradiation.

According to the present invention, a near-infrared ray absorbing agent having a high gram absorption coefficient can be provided.

10‧‧‧矽 substrate

12‧‧‧Photographic components

13‧‧‧Interlayer insulating film

14‧‧‧Material layer

15R‧‧‧Red color filter

15G‧‧‧Green color filter

15B‧‧‧Blue color filter

16‧‧‧Overcoat

17‧‧‧Microlens

18‧‧‧Shade film

20, 45‧‧‧Adhesive

22‧‧‧Insulation film

23‧‧‧Metal electrodes

24‧‧‧solder layer

26‧‧‧Internal electrodes

27‧‧‧Component surface electrode

30‧‧‧ glass substrate

40‧‧‧ camera lens

42‧‧‧Near-infrared cut-off filter

44‧‧‧Shading and electromagnetic shielding

46‧‧‧Destivation layer

50‧‧‧ lens holder

60‧‧‧ solder balls

70‧‧‧ circuit board

100‧‧‧Solid imaging element substrate

200‧‧‧ camera module

Hν‧‧‧ incident light

FIG. 1 is a schematic cross-sectional view showing a configuration of an image pickup module including a solid-state image sensor according to an embodiment of the present invention.

2 is a schematic cross-sectional view showing a solid-state imaging element substrate according to an embodiment of the present invention.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be performed according to a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In addition, the numerical range represented by "~" in this specification is the range which contains the numerical value of the [----

In the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic acid and methacrylic acid, and "(meth)acryloyl group" means propylene. Mercapto and methacrylonitrile. In addition, in this specification, "monomer" and "monomer" have the same meaning. The monomer in the present invention means a compound having a weight average molecular weight of 2,000 or less which is distinguished from an oligomer and a polymer. Compound. 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. Further, in the expression of the group (atomic group) in the present specification, the substituted and unsubstituted expressions are not described as including a group having no substituent, and also a group having 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).

In the present invention, the term "near infrared ray" means a maximum absorption wavelength in the range of 700 nm to 2500 nm.

The phosphate compound in the present specification means a phosphate monoester compound, a phosphodiester compound or a mixture thereof.

The near-infrared ray absorbing agent of the present invention is characterized by containing a copper phosphate complex which is obtained by reacting a phosphodiester compound represented by the following formula with a copper salt.

(In the above, R is an organic group; O = P-O angle is in the range of 104 to 120 degrees)

By thus reducing the O=P-O angle, the resulting copper complex can be deformed to increase the gram extinction coefficient.

In the present invention, the O=P-O angle is preferably less than 110 degrees, more preferably 104 degrees. ~109.5 degrees. By setting it as such a range, a near-infrared absorbing agent more suitable for the near-infrared cut-off layer can be produced.

In the present invention, the O-P-O angle of the phosphodiester compound is preferably from 104 to 120 degrees, more preferably from 104 to 109.5 degrees. The O-P-O angle of the phosphodiester compound is usually in the above range by adjusting the O=P-O angle of the phosphodiester compound.

In the present invention, a phosphate monoester compound may also be contained as a phosphate compound which reacts with a copper salt. The phosphoric acid monoester compound is also preferably an O = P-O angle of less than 110 degrees, more preferably from 104 to 109.5 degrees. By setting it as such a range, a near-infrared absorbing agent more suitable for the near-infrared cut-off layer can be produced.

The chrome absorption coefficient of the copper phosphate complex of the present invention is preferably 0.03 g/ml or more, more preferably 0.05 g/ml or more.

Among them, the gram absorption coefficient is the absorbance/concentration (the so-called concentration means the weight (g) per 1 mL).

Further, the maximum absorption wavelength of the copper phosphate complex is preferably from 104 nm to 120 nm, more preferably from 104 nm to 109.5 nm.

The phosphoric acid monoester compound used in the present invention is preferably a compound represented by the following formula (1). Further, the phosphodiester compound used in the present invention is preferably a compound represented by the following formula (2).

Formula 1)

(In the formulae (1) and (2), R is an organic group having 3 or more carbon atoms. Further, in the formula (2), R may be bonded to each other to form a cyclic structure, and in this case, The total number of carbon atoms in the group of the ring-shaped cyclic structure is 3 or more)

In the formulae (1) and (2), R is an organic group having 3 or more carbon atoms, preferably a carbon number of 5 or more, and more preferably an organic group having 5 to 20 carbon atoms.

Further, in the formula (2), R may be bonded to each other to form a cyclic structure, and in this case, the total number of carbon atoms of the group including the bonded cyclic structure is 3 or more, preferably The carbon number is 5 or more, and more preferably an organic group having 5 to 20 carbon atoms.

R in the above formula (1) and formula (2) is preferably a group selected from the group consisting of an organic group having a (meth)acryloxy group as a substituent, a secondary alkyl group having an alkyl group as a substituent, A tertiary alkyl group having an alkyl group as a substituent, an aryl group having a substituent, and one or more organic groups having a cyclic structure in which R is bonded to each other.

The organic group having a (meth)acryloxy group as a substituent deforms in the formed complex by a steric hindrance or a mechanism derived from electron repulsion of a double bond site and an oxygen atom.

The organic group having a (meth) acryloxy group as a substituent may have one (meth) acryloxy group in one R and may have two or more (meth) acryloxy groups. Usually, one or two (meth)acryloxy groups are contained in one R. The organic group having a (meth)acryloxy group as a substituent is preferably an alkyl group having a (meth)acryloxy group as a substituent. The organic group having a (meth)acryloxy group as a substituent may further contain a substituent other than the (meth) acryloxy group, and preferably contains only a (meth) acryloxy group as a substituent. When the (meth)acryloyloxy group-substituted organic group is an alkyl group, the alkyl chain preferably has 2 to 6 carbon atoms.

Since the secondary alkyl group having an alkyl group as a substituent and the tertiary alkyl group having an alkyl group as a substituent have a large volume structure, deformation occurs in the formed complex by steric hindrance. Here, the secondary alkyl group having an alkyl group as a substituent means a group represented by -CHR' ₂ (R' is a substituent and at least one is an alkyl group), and the third group having an alkyl group as a substituent The alkyl group means a group represented by -CR' ₃ (R' is a substituent and at least one is an alkyl group). R' is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group or a branched alkyl group having 3 to 5 carbon atoms. R' is preferably an isopropyl group or an alkyl group having an isopropyl group at the terminal. Therefore, the secondary alkyl group having an isopropyl group as a substituent and the tertiary alkyl group having an isopropyl group as a substituent means that the above R' is an isopropyl group or an alkyl group having an isopropyl group at the terminal. R' is preferably a total carbon number of from 1 to 10.

Since the aryl group having a substituent has a large volume structure, deformation occurs in the formed complex by steric hindrance.

The substituent which the aryl group has is not particularly limited as long as it is an organic group, and examples thereof include an ester group and the like.

Any one or more organic groups containing a cyclic structure in which R is bonded to each other are deformed in the formed complex by a steric hindrance or a straightening mechanism of a structure due to ring formation .

In the case where R forms a cyclic structure, one atom constituting the ring is a phosphorus atom, and at least two atoms are oxygen atoms. The cyclic structure is preferably composed of one phosphorus atom, two oxygen atoms, and two to four carbon atoms. Further, the cyclic structure may have a substituent.

Any one or more organic groups containing a cyclic structure in which R is bonded to each other have a total carbon number of 3 or more, preferably 3 to 10.

R is preferably composed of an atom selected from a carbon atom, an oxygen atom, a hydrogen atom, a sulfur atom, and a nitrogen atom, more preferably an atom selected from a carbon atom, an oxygen atom, a hydrogen atom, or a sulfur atom. Further, it is preferably composed of an atom selected from a carbon atom, an oxygen atom, and a hydrogen atom. Further, the total value of the carbon atom, the oxygen atom, the sulfur atom, and the nitrogen atom is preferably 5 to 30.

Hereinafter, examples of the phosphate compound which can be used in the present invention are shown, but the present invention is of course not limited to these examples.

A-9

A-14

The phosphate compound used in the present invention can be synthesized, for example, by the following method.

<Synthesis of the following compounds>

Triethylamine was added to a solution of 2,4-dimethylpentanol in tetrahydrofuran (THF), stirred at 0 ° C for 5 minutes, and phosphorus oxychloride was added dropwise, followed by stirring at room temperature for 6 hours. Thereby the reaction is ended. After the completion of the reaction, the reaction solution was decanted with water so that the temperature did not rise to 30 ° C or higher. The liquid was separated by chloroform/water, and the solvent of the organic layer was distilled off, whereby the following phosphate ester was obtained.

In the present invention, a phosphate compound is reacted with a copper salt to form a copper phosphate complex. The copper phosphate complex is usually formed by stirring a phosphate compound with a copper salt.

The phosphate compound is a phosphodiester compound, but may be a mixture of a phosphodiester compound and a phosphoric acid monoester compound. In the case of using both the compound represented by the formula (1) and the compound represented by the formula (2), the mixing ratio is preferably, for example, the molar ratio of the compound represented by the formula (1): represented by the formula (2) The molar ratio of the compound is 0.2 to 0.8: 0.8 to 0.2, more preferably 0.3 to 0.7: 0.7 to 0.3, and further preferably 0.4 to 0.6: 0.6 to 0.4.

Further, as a commercially available product, for example, Phosmer M, Phosmer PE, and Phosmer PP (Uni-Chemical) may be used in the synthesis of the copper phosphate compound. ) (manufactured by the company)).

The copper salt used herein is preferably divalent copper or trivalent copper, more preferably divalent copper. The copper salt is more preferably copper acetate, copper chloride, copper formate, copper stearate, copper benzoate, copper ethylacetate, copper pyrophosphate, copper naphthenate, copper citrate, copper nitrate, copper sulfate, Copper carbonate, copper chlorate, copper (meth)acrylate, and further preferably copper benzoate or copper (meth)acrylate.

The near-infrared absorbing agent of the present invention can be preferably used by being incorporated into a near-infrared absorbing composition for forming a near-infrared cut-off layer. In the case of blending into a near-infrared absorbing composition, it is possible to adjust only one kind of near-infrared rays of the present invention. As the absorbent, two or more kinds of near-infrared absorbing agents of the present invention may be formulated.

The compounding amount of the copper phosphate complex in the near-infrared absorbing composition is such that the copper phosphite complex is contained in the near-infrared absorbing composition in an amount of 10% by mass to 80% by mass, preferably 15%. The copper phosphate complex of % to 70% by mass, more preferably 20% to 50% by mass of the copper phosphate complex.

In addition, the compounding amount of the copper phosphate complex compound contains a copper phosphate complex compound in a ratio of 35% by mass to 90% by mass, preferably 40% by mass, based on the solid content of the near-infrared absorbing composition. The % to 90% by mass of the copper phosphate complex is more preferably from 45% by mass to 87% by mass of the copper phosphate complex.

Next, the near-infrared absorbing composition of the present invention (hereinafter sometimes referred to as "the composition of the present invention") will be described. The composition of the present invention may contain a component such as a curable compound, a polymerization initiator, a solvent, and a surfactant in addition to the near-infrared ray absorbing agent. Hereinafter, the components will be described.

<hardening compound>

The composition of the present invention usually contains a curable compound. However, in the case where the copper complex itself has a polymerizable group or the like and is a curable compound, a curable compound is not necessarily required. The curable compound may be a polymerizable compound or a non-polymerizable compound such as a binder. Further, it may be a thermosetting compound or a photocurable compound.

<Polymerizable compound>

The composition of the present invention preferably contains a compound having a polymerizable group (hereinafter sometimes referred to as "polymerizable compound"). This group of compounds is in the industry It is widely known that these compounds can be used without particular limitation in the present invention. These compounds may be, for example, any of chemical forms such as monomers, oligomers, prepolymers, and polymers.

The polymerizable compound may be monofunctional or polyfunctional, preferably polyfunctional. By containing a polyfunctional compound, near-infrared shielding properties and heat resistance can be further improved. The number of functional groups is not particularly limited, but is preferably a bifunctional to an octafunctional.

<<A: Polymerizable monomer and polymerizable oligomer>>

The first preferred embodiment of the composition of the present invention is a monomer (polymerizable monomer) having a polymerizable group or an oligomer (polymerizable oligomer) having a polymerizable group (hereinafter, polymerizability is sometimes used) The monomer and the polymerizable oligomer are collectively referred to as "polymerizable monomer or the like" as a polymerizable compound.

Examples of the polymerizable monomer and the like include an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methacrylic acid, maleic acid, etc.) or an ester thereof or a guanamine, preferably An ester of an unsaturated carboxylic acid and an aliphatic polyol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound. Further, an addition reaction of an unsaturated carboxylic acid ester or a guanamine having a nucleophilic substituent such as a hydroxyl group or an amine group or a fluorenyl group with a monofunctional or polyfunctional isocyanate or epoxy group, or a monofunctional or polyfunctional group A dehydration condensation reaction product of a carboxylic acid or the like can also be preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or an oxime amine having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol, A substituted reactant of an unsaturated carboxylic acid ester or a guanamine having a detachable substituent such as a halogen group or a tosyloxy group and a monofunctional or polyfunctional alcohol, an amine or a thiol is also preferred. Further, as another example, a compound group obtained by replacing with a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, vinyl ether or allyl ether may be used instead of the above unsaturated carboxylic acid.

For the specific compound, the compound described in Paragraph No. 0095 to Paragraph No. 0108 of JP-A-2009-288705 is also preferably used in the present invention.

Further, the polymerizable monomer or the like is preferably a compound having an ethylenically unsaturated group having at least one vinyl group capable of undergoing addition polymerization and having a boiling point of 100 ° C or higher at normal pressure. Examples thereof include monofunctional acrylates or methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate; Ethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(a) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, hexane diol (meth) acrylate, trimethylolpropane tris(propylene oxypropyl) ether Addition of ethylene (Ethylene Oxide, EO) or propylene oxide to polyfunctional alcohol such as glycerol or trimethylolethane, or isopropane cyanurate (Ethylene Oxide, EO) or propylene oxide ( (Methyl)acrylic acid (meth)acrylic acid as described in each of the Japanese Patent Publication No. Sho-48-41708, the Japanese Patent Publication No. Sho. Aminoformates; Japanese Patent Laid-Open No. 48-64183, Japanese Patent No. Sho 49-43191, Japanese Patent Special No. 5 Polyester acrylates described in each of the publications No. 2-30490; epoxy as a reaction product of an epoxy polymer and (meth)acrylic acid A polyfunctional acrylate or methacrylate such as an acrylate or a mixture thereof.

Further, a polyfunctional (meth) acrylate or the like, and the polyfunctional (meth) acrylate is a compound having a cyclic ether group and an ethylenically unsaturated group such as glycidyl (meth)acrylate, and a polyfunctional carboxy group. Obtained by acid reaction.

In addition, as another preferable polymerizable monomer, an ethylenic ring having an anthracene ring and having two or more functional groups described in JP-A-2010-160418, JP-A-2010-129825, and Japanese Patent No. 4,364,216, etc., may be used. A polymerizable group compound or a cardo polymer.

Further, a compound having a boiling point of 100 ° C or higher and having at least one ethylenically unsaturated group capable of undergoing addition polymerization under normal pressure is also preferably a paragraph number [0254] of JP-A-2008-292970. The compound described in paragraph No. [0257].

In addition, the following compounds can also be used as a polymerizable monomer: as described in JP-A No. 10-62986, the general formula (1) and the general formula (2) are described together with the specific examples, and the above polyfunctional alcohol is added. A compound obtained by esterification of ethylene oxide or propylene oxide with (meth) acrylate.

The polymerizable monomer used in the present invention is more preferably a polymerizable monomer represented by the following formula (MO-1) to formula (MO-6).

R= , , ,-OH,-CH ₃

T=-(CH ₂ ) _m -, -OCH ₂ -, -O(CH ₂ ) ₂ -, -O(CH ₂ ) ₃ -, -O(CH ₂ ) ₄ -

Z=

(wherein, n is 0 to 14, respectively, and m is 1 to 8. Each of R, T, and Z in a molecule may be the same or different. When T is an oxygen-extended alkyl group, the carbon atom The end of the side is bonded to R. At least one of R is a polymerizable group)

n is preferably 0 to 5, more preferably 1 to 3.

m is preferably from 1 to 5, more preferably from 1 to 3.

R is preferably Better

Specific examples of the radical polymerizable monomer represented by the above formula (MO-1) to (MO-6) can be described in paragraph number 0248 to paragraph number 0251 of JP-A-2007-269779. The recited compounds are also preferably used in the present invention.

Among them, the polymerizable monomer or the like is preferably dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available product) KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercial product is KAYARAD D-310; Nippon Chemical Co., Ltd. Manufactured by the company), dipentaerythritol hexa(meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), and (meth) acrylonitrile-based spacers of these compounds The structure of the ethylene glycol or propylene glycol residue, or the diglycerin ethylene oxide modified (meth) acrylate (commercially available as M-460; manufactured by Toagosei Co., Ltd.). These oligomer types can also be used.

For example, RP-1040 (made by Nippon Kayaku Co., Ltd.) or the like can be mentioned.

The polymerizable monomer or the like may also be a polyfunctional monomer, and may also have a carboxyl group or a sulfonate. An acid group such as an acid group or a phosphoric acid group. Therefore, the ethylenic compound may be used as it is in the case of a mixture as described above, and may be used as it is, and if necessary, a non-aromatic carboxylic anhydride may be reacted with a hydroxyl group of the above-mentioned ethylenic compound to introduce an acid group. In this case, specific examples of the non-aromatic carboxylic anhydride to be used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and alkylated six. Hydrogen phthalic anhydride, succinic anhydride, maleic anhydride.

In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and preferably has a non-aromatic carboxylic anhydride reacting with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to have an acid group. The polyfunctional monomer, particularly preferably in its ester, the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. For example, M-305, M-510, M-520, etc. of the Aronix series which is a polyacid-modified acryl-type oligomer manufactured by the East Asia Synthetic Co., Ltd. can be mentioned.

The preferred acid value of the polyfunctional monomer having an acid group is from 0.1 mg-KOH/g to 40 mg-KOH/g, and more preferably from 5 mg-KOH/g to 30 mg-KOH/g. In the case where a polyfunctional monomer having two or more acid groups is used in combination or a polyfunctional monomer having no acid group is used in combination, it is necessary to prepare in such a manner that the acid value of the entire polyfunctional monomer is within the above range.

Further, a polyfunctional monomer having a modified structure of caprolactone is preferably used as a polymerizable monomer or the like.

The polyfunctional monomer having a caprolactone-modified structure is not particularly limited as long as it has a caprolactone-modified structure in its molecule, and examples thereof include ε-caprolactone-modified polyfunctional (meth) acrylate. , the ε-caprolactone modified polyfunctional (meth) acrylate By trimethylolethane, di-trimethylolethane, trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol, trishydroxyl A polyol such as melamine is obtained by esterification with (meth)acrylic acid and ε-caprolactone. Among them, a polyfunctional monomer having a caprolactone modified structure represented by the following formula (1) is preferred.

(In the formula, all of the six R groups are groups represented by the following formula (2), or one to five of the six R groups are groups represented by the following formula (2), and the rest are the following formulas ( 3) the indicated group)

(wherein R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bond)

(wherein R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bond)

Such a polyfunctional monomer having a modified structure of caprolactone is commercially available, for example, as a KAYARAD DPCA series from Nippon Kayaku Co., Ltd., and may be exemplified by DPCA-20 (the above formula (1) In the formula (3), m = 1, the number of groups represented by the formula (2) = 2, and the compound in which all R ¹ are a hydrogen atom), and DPCA-30 (in the above formula (1) to formula (3) m = 1, the number of groups represented by the formula (2) = 3, a compound in which all of R ¹ is a hydrogen atom), and DPCA-60 (m = 1, in the above formula (1) to formula (3), 2) The number of the groups shown is =6, the compound in which all of R ¹ is a hydrogen atom), and DPCA-120 (m=2 in the above formula (1) to formula (3), and the group represented by formula (2) The number of the groups = 6, the compound in which all of R ¹ are a hydrogen atom) and the like.

In the present invention, the polyfunctional monomer having a modified structure of caprolactone may be used alone or in combination of two or more.

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

In the above formula (i) and formula (ii), E independently represents -((CH ₂ )yCH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)-, y are each independently The ground represents an integer of 0 to 10, and X each independently represents an acryloyl group, a methacrylinyl group, a hydrogen atom or a carboxyl group.

In the above formula (i), the total of the acryloyl group and the methacryl fluorenyl group is 3 or 4, and m each independently represents an integer of 0 to 10, and the total value of each m is an integer of 0 to 40. However, when the total value of each m is 0, any one of X is a carboxyl group.

In the above formula (ii), the total of the acrylonitrile group and the methacryl group is 5 or 6, and n each independently represents an integer of 0 to 10, and the total value of each n is an integer of 0 to 60. However, when the total value of each n is 0, any one of X is a carboxyl group.

In the above formula (i), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the total value of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.

In the above formula (ii), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the total value 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.

Further, -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)- in the formula (i) or the formula (ii) is preferably on the oxygen atom side The end is bonded to the form of X.

The compound represented by the above formula (i) or (ii) may be used alone or in combination of two or more. It is especially preferred that all of the six X in the formula (ii) are in the form of an acrylonitrile group.

The compound represented by the above formula (i) or formula (ii) can be synthesized by the following steps as a previously known step: a ring-opening skeleton is obtained by subjecting ethylene oxide or propylene oxide to a ring-opening addition reaction. A step of bonding to pentaerythritol or dipentaerythritol; and reacting, for example, (meth)acrylofluorene chloride with a terminal hydroxyl group of the ring-opening skeleton to introduce a (meth)acrylonitrile group. Each step is a well-known step, and a compound represented by the formula (i) or the formula (ii) can be easily synthesized by those skilled in the art.

Among the compounds represented by the above formula (i) or formula (ii), a pentaerythritol derivative and/or a dipentaerythritol derivative are more preferred.

Specific examples thereof include the compounds represented by the following formulas (a) to (f) (hereinafter also referred to as "exemplary compounds (a) to exemplified compounds (f)"). Among them, preferred examples are compounds (a) and exemplified. Compound (b), exemplified compound (e), and exemplified compound (f).

Commercial product such as a polymerizable monomer represented by the general formula (i) or the general formula (ii) For example, a tetrafunctional acrylate SR-494 having four ethoxylated chains manufactured by Sartomer Co., Ltd., and a hexafunctional acrylic acid having six pentyloxy chains manufactured by Nippon Kayaku Co., Ltd. can be cited. The ester DPCA-60, a trifunctional acrylate TPA-330 having three isobutyoxy chains, and the like.

In addition, the polymerizable monomer and the like are also preferably described in Japanese Patent Publication No. Sho 48-41708, Japanese Patent Laid-Open No. Sho 51-37193, Japanese Patent Laid-Open No. 2-32293, and Japanese Patent Publication No. Hei 2-16765. The urethane amides, or the epoxy resins described in Japanese Patent Publication No. Sho 58-49860, Japanese Patent Publication No. Sho 56-17654, Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-39418 A urethane compound of an ethane-based skeleton. Further, an amine group structure or a sulfide structure is contained in the molecule as described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. As the polymerizable monomer, an addition polymerizable monomer can obtain a curable composition having a very excellent photospeed.

A commercially available product such as a polymerizable monomer may, for example, be a urethane oligomer UAS-10 or a urethane oligomer UAB-140 (manufactured by Sanyo-Kokusaku Pulp Co., Ltd.), 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 Kyoei Co., Ltd.) Wait.

The polymerizable monomer or the like is also preferably a polyfunctional thiol compound having two or more mercapto (SH) groups in the same molecule. More preferably, it is a compound represented by the following formula (I).

(wherein R ¹ represents an alkyl group, R ² represents an n-valent aliphatic group which may contain an atom other than carbon, R ⁰ represents an alkyl group other than H, and n represents 2 to 4)

Specific examples of the polyfunctional thiol compound represented by the above formula (I) include 1,4-bis(3-mercaptobutyloxy)butane having the following structural formula [Formula (II) ], 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione [formula (III)] And pentaerythritol tetrakis(3-mercaptobutyrate) [formula (IV)] and the like. These polyfunctional thiols may be used alone or in combination of two or more.

In the present invention, it is also preferred to use two or more rings in the molecule. A polymerizable monomer or oligomer of an oxy or oxetanyl group is used as a polymerizable monomer. Specific examples of these will be collectively described in the section of the compound having an epoxy group or an oxetanyl group which will be described later.

<<B: Polymer having a polymerizable group in a side chain>>

A second preferred embodiment of the composition of the present invention is a form containing a polymer having a polymerizable group in a side chain as a polymerizable compound.

The polymerizable group may, for example, be an ethylenically unsaturated double bond group, an epoxy group or an oxetanyl group.

The latter will be collectively described in the section of the compound having an epoxy group or an oxetanyl group described later.

The polymer having an ethylenically unsaturated bond in the side chain is preferably a polymer compound having a functional group selected from any one of the following general formulae (1) to (3). At least one part as an unsaturated double bond.

In the above formula (1), R ¹ to R ³ each independently represent a hydrogen atom or a monovalent organic group, and R ¹ preferably includes a hydrogen atom or an alkyl group which may have a substituent, and the like, wherein a radical reaction In terms of high properties, a hydrogen atom or a methyl group is preferred. Further, R ² and R ³ each independently include a hydrogen atom, a halogen atom, an amine group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, and may have a substituent. Aryl group, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, arylamino group which may have a substituent, alkylsulfon which may have a substituent An anthracenyl group, an arylsulfonyl group which may have a substituent, etc., and a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, etc. are preferable in terms of a high radical reactivity. An aryl group having a substituent.

X represents an oxygen atom, a sulfur atom or -N(R ¹² )-, and R ¹² represents a hydrogen atom or a monovalent organic group. In the above, R ¹² may be an alkyl group which may have a substituent, and among them, a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group is preferable in terms of high radical reactivity.

Here, the substituent which can be introduced may, for example, be an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an amine group, an alkylamino group, an arylamine group, a carboxyl group or an alkane. An oxycarbonyl group, a sulfo group, a nitro group, a cyano group, a decylamino group, an alkylsulfonyl group, an arylsulfonyl group or the like.

In the above formula (2), R ⁴ to R ⁸ each independently represent a hydrogen atom or a monovalent organic group, and R ⁴ to R ⁸ preferably include a hydrogen atom, a halogen atom, an amine group, a dialkylamine group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, 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, an arylamine group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, etc., among which a hydrogen atom is preferred And a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent.

The substituent which can be introduced can be exemplified by the same formula (1). Further, Y represents an oxygen atom, a sulfur atom or -N(R ¹² )-. Case R R ¹² in the general formula (1) ¹² is the same meaning, the preferred embodiments are also the same.

In the above 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 is preferred in terms of high radical reactivity. R ¹⁰ and R ¹¹ each independently include a hydrogen atom, a halogen atom, an amine group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, 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, an arylamine group which may have a substituent, may have a substituent The alkylsulfonyl group, the arylsulfonyl group which may have a substituent, etc., wherein, in terms of high radical reactivity, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, or a substituent may be preferable. An alkyl group, an aryl group which may have a substituent.

Here, the substituent which can be introduced can be exemplified by the same formula (1). Further, Z represents an oxygen atom, a sulfur atom, -N(R ¹³ )- or a stretched phenyl group which may have a substituent. R ¹³ may, for example, be an alkyl group which may have a substituent, and among them, a methyl group, an ethyl group, and an isopropyl group are preferable in terms of high radical reactivity.

The polymer having an ethylenically unsaturated bond in the side chain of the present invention is preferably a compound having the above formula in a range of 20 mol% or more and less than 95 mol% in one molecule. 1) to a structural unit of a functional group represented by the formula (3). More preferably, it is 25 mol% - 90 mol%. Further, it is preferably in the range of 30 mol% or more and less than 85 mol%.

The synthesis of the polymer compound having a structural unit containing the group represented by the above formula (1) to the formula (3) can be carried out according to the paragraph number [0027] to paragraph number [0057] of JP-A-2003-262958. The synthesis method described in ] is carried out. Among them, the synthesis method 1) in JP-A-2003-262958 is preferably used.

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 means a dissociative group having a pKa of 14 or less, and specific examples thereof include -COOH, -SO ₃ H, -PO ₃ H ₂ , -OSO ₃ H, and -OPO _{2 .} H ₂ , -PhOH, -SO ₂ H, -SO ₂ NH ₂ , -SO ₂ NHCO-, -SO ₂ NHSO ₂ -, etc., among which -COOH, -SO ₃ H, -PO ₃ H _{2 are} preferred, and further Good for -COOH.

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

The polymer having a carboxyl group may, for example, be 1) a polymer obtained by subjecting a monomer having a carboxyl group to radical polymerization or ion polymerization; 2) subjecting a monomer having an acid anhydride to radical or ionic polymerization and hydrolyzing an acid anhydride unit or a half A polymer obtained by esterification; 3) an epoxy acrylate obtained by modifying an epoxy polymer with an unsaturated monocarboxylic acid and an acid anhydride.

Specific examples of the vinyl polymer having a carboxyl group include (meth)acrylic acid, 2-bromodecyloxyethyl methacrylate, and 2-maleyloxyethyl methacrylate. , 2-phthalic acid ethyl methacrylate, 2-hexahydrophthalic acid ethyl methacrylate, maleic acid, fumaric acid, itaconic acid, crotonic acid, etc. a saturated carboxylic acid as a polymer obtained by homopolymerization of a monomer having a carboxyl group, or a mixture of the unsaturated carboxylic acid and styrene, α-methylstyrene, methyl (meth)acrylate, or (meth)acrylic acid Ethyl ester, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, vinyl acetate, acrylonitrile, (meth) acrylamide, glycidol (meth) acrylate Ester, allyl glycidyl ether, glycidyl ethacrylate, glycidyl crotonate, (meth) acrylonitrile, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, N- Hydroxymethyl acrylamide, N,N-dimethyl decylamine, N-methylpropenyl morpholine, N,N-dimethylaminoethyl (meth) acrylate, N, N- two Yl aminoethyl acrylamide monomer and other vinyl-based polymer having no carboxyl groups is obtained by copolymerization.

Further, maleic anhydride may be copolymerized with styrene or α-methylstyrene, and maleic anhydride may be used as a monohydric alcohol such as methanol, ethanol, propanol, butanol or hydroxyethyl (meth)acrylate. Semi-esterification of unit moieties or maleic anhydride units by water Partially hydrolyzed polymer.

In the above, a polymer having a carboxyl group is preferred, and a (meth)acrylic (co)polymer containing (meth)acrylic acid is preferred. Examples of the copolymers include, for example, Japanese Patent Special Opening Methyl methacrylate/methacrylic acid copolymer described in JP-A-60-214354, and methyl methacrylate/methyl acrylate/methacrylic acid copolymer described in JP-A-60-214354, Japanese Patent Application No. Benzyl methacrylate/methyl methacrylate/methacrylic acid/2-ethylhexyl acrylate copolymer described in JP-A-H05-36581, and methyl methacrylate described in JP-A-H05-333542 / n-butyl methacrylate / 2-ethylhexyl acrylate / methacrylic acid copolymer, styrene / methyl methacrylate / methyl acrylate / methacrylic acid copolymer described in Japanese Patent Laid-Open No. Hei 7-261407 Methyl methacrylate/n-butyl acrylate/2-ethylhexyl acrylate/methacrylic acid copolymer described in Japanese Laid-Open Patent Publication No. Hei 10-110008, and the Japanese Patent Publication No. Hei 10-198031 Methyl acrylate/propylene N-butyl acrylate / 2-ethylhexyl acrylate / styrene / methacrylic acid copolymer.

The polymer having an acid group and a polymerizable group in the side chain in the present invention is preferably a polymer compound having a compound selected from the following general formulae (1-1) to (3-1). At least one of the structural units represented is an unsaturated double bond moiety.

In the above formula (1-1) to formula (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 a substitutable substituent. Alkyl group. 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 stretched phenyl 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 represent a monovalent substituent.

In the above formula (1-1), R ¹ to R ³ each independently represent a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may have a substituent, and wherein R ¹ and R ^{2 are} preferably hydrogen. The atom, R ^{3 is} preferably a hydrogen atom or a methyl group.

R ⁴ to R ⁶ each independently represent a monovalent substituent, and R ⁴ may, for example, be a hydrogen atom or an alkyl group which may have a more substituent, and among them, a hydrogen atom, a methyl group and an ethyl group are preferable. Further, R ⁵ and R ⁶ each independently include a hydrogen atom, a halogen atom, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, and an aryl group which may have a more substituent group. An alkoxy group which may have a substituent, an aryloxy group which may have a more substituent, an alkylsulfonyl group which may have a more substituent, an arylsulfonyl group which may have a more substituent, etc., among which, It is a hydrogen atom, an alkoxycarbonyl group, an alkyl group which may have a more substituent, and an aryl group which may have a more substituent.

Here, examples of the substituent which can be introduced include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, a methyl group, an ethyl group, a phenyl group and the like.

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, R ²¹ and R ²² may, for example, be an alkyl group which may have a substituent.

G ¹ represents a divalent organic group, preferably an alkylene group which may have a substituent. More preferably, an alkylene group having a substituent of 1 to 20 carbon atoms, a stretched alkyl group having 3 to 20 carbon atoms, a ring-shaped alkyl group having a substituent of 6 to 20 carbon atoms, and the like having a substituent group may be mentioned. Among them, in terms of properties such as strength and developability, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent and a ring having a substituent having 3 to 10 carbon atoms are preferable. An alkyl group or an aromatic group having 6 to 12 carbon atoms which may have a substituent.

Here, the substituent of G ¹ is preferably a hydroxyl group.

In the above formula (2-1), R ⁷ to R ⁹ each independently represent a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may have a substituent, and wherein R ⁷ and R ^{8 are} preferably hydrogen. The atom, R ^{9 is} preferably a hydrogen atom or a methyl group.

R ¹⁰ to R ¹² each independently represent a monovalent substituent, and specific examples thereof include a hydrogen atom, a halogen atom, a dialkylamino group, an alkoxycarbonyl group, a sulfo group, a nitro group, and a cyano group. An alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a more substituent, an aryloxy group which may have a more substituent, and an alkylsulfonyl group which may have a more substituent Further, an arylsulfonyl group which may have a substituent, and the like, among them, a hydrogen atom, an alkoxycarbonyl group, an alkyl group which may have a more substituent group, and an aryl group which may have a more substituent group are preferable.

Here, the substituent which can be introduced can be similarly exemplified in the formula (1-1).

A ² each independently represents an oxygen atom, a sulfur atom or -N(R ²¹ )-. Here, R ²¹ may, for example, be a hydrogen atom or an alkyl group which may have a substituent.

G ² represents a divalent organic group, and preferably an alkylene group which may have a substituent. Preferred examples thereof include an alkylene group having a substituent of 1 to 20 carbon atoms, a stretched alkyl group having 3 to 20 carbon atoms and a ring-shaped alkyl group having a substituent of 6 to 20 carbon atoms, and the like. Among them, in terms of properties such as strength and developability, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent and a ring having a substituent having 3 to 10 carbon atoms are preferable. An alkyl group or an aromatic group having 6 to 12 carbon atoms which may have a substituent.

Here, the substituent of G ² is preferably a hydroxyl group.

Y represents an oxygen atom, a sulfur atom, -N(R ²³ )- or a stretched phenyl group which may have a substituent. Here, R ²³ may, for example, be a hydrogen atom or an alkyl group which may have a substituent.

In the above formula (3-1), R ¹³ to R ¹⁵ each independently represent a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may have a substituent. Among them, R ¹³ and R ^{14 are} preferably a hydrogen atom. R ^{15 is} preferably a hydrogen atom or a methyl group.

R ¹⁶ to R ²⁰ each independently represent a monovalent substituent, and examples of R ¹⁶ to R ²⁰ include a hydrogen atom, a halogen atom, a dialkylamino group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, and the like. a more substituted alkyl group, a more substituted aryl group, a more substituted alkoxy group, a more substituted aryloxy group, a more substituted alkyl sulfonyl group, Further, an arylsulfonyl group or the like having a substituent is preferably a hydrogen atom, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a more substituent. The substituent which can be introduced can be exemplified by the 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 )-. R ²¹ and R ²² may be the same as those in the formula (1).

G ³ represents a divalent organic group, preferably an alkylene group which may have a substituent. Preferred examples thereof include an alkylene group having a substituent of 1 to 20 carbon atoms, a stretched alkyl group having 3 to 20 carbon atoms and a ring-shaped alkyl group having a substituent of 6 to 20 carbon atoms, and the like. Among them, in terms of properties such as strength and developability, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent and a ring having a substituent having 3 to 10 carbon atoms are preferable. An alkyl group or an aromatic group having 6 to 12 carbon atoms which may have a substituent.

Here, the substituent of G ³ is preferably a hydroxyl group.

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

The polymer having an acid group and an ethylenically unsaturated bond in the side chain of the present invention preferably has an acid value of from 20 to 300, preferably from 40 to 200, more preferably from 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 "amino carboxylic acid" Ester polymer").

The urethane polymer is a polyurethane polymer having a structural unit as a basic skeleton (hereinafter referred to as "specific polyurethane polymer" as appropriate), and the above structural unit is represented by the following formula (4) A reaction product of at least one of the diisocyanate compounds represented by the formula (5) and at least one of the diol compounds represented by the formula (5).

OCN-X ⁰ -NCO General formula (4)

HO-Y ⁰ -OH general formula (5)

In the general formulae (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 above formula (4) or the diol compound represented by the formula (5) has the above formula (1) to formula (exhibit) which exhibits an unsaturated double bond moiety ( 3) at least one of the groups represented by the formation of a specific polyurethane polymer having a group represented by the above formula (1) to formula (3) introduced into the side chain as the The reaction product of a diisocyanate compound and the diol compound. According to this method, the specific polyurethane polymer of the present invention can be more easily produced by performing substitution and introduction of a desired side chain after the reaction of the polyurethane polymer is formed.

1) Diisocyanate compound

The diisocyanate compound represented by the above formula (4) is, for example, a product obtained by subjecting a triisocyanate compound to a monofunctional alcohol having an unsaturated group or a monofunctional amine compound in an amount of 1 equivalent.

Examples of the triisocyanate compound include the following, but are not limited thereto.

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

Here, the method of introducing an unsaturated group into the side chain of the polyurethane polymer is preferably a method of using a diisocyanate compound having an unsaturated group in a side chain as a polyurethane. The raw material of the polymer. The diisocyanate compound which can be obtained by an addition reaction of a triisocyanate compound with a monofunctional alcohol or a monofunctional amine compound having an unsaturated group, and has an unsaturated group in a side chain, for example, may be exemplified below. The one shown is not limited to this.

For example, the specific polyurethane resin used in the present invention can impart the above unsaturated group-containing diisocyanate from the viewpoint of improving compatibility with other components in the polymerizable composition, improving storage stability, and the like. The diisocyanate compound other than the compound is copolymerized.

The diisocyanate compound to be copolymerized may be exemplified below. A diisocyanate compound represented by the following formula (6) is preferred.

OCN-L ¹ -NCO General formula (6)

In the formula (6), L ¹ represents a divalent aliphatic or aromatic hydrocarbon group which may have a substituent. If desired, L ¹ may also have other functional groups which do not react with isocyanate groups, such as esters, urethanes, guanamines, ureido groups.

The diisocyanate compound represented by the above formula (6) specifically includes the following.

That is, for example, a dimer of 2,4-toluene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 4,4' An aromatic diisocyanate compound such as diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate or 3,3'-dimethylbiphenyl-4,4'-diisocyanate; such as hexamethylene diisocyanate An aliphatic diisocyanate compound such as trimethylhexamethylene diisocyanate, diazonic acid diisocyanate or dimer acid diisocyanate; such as isophorone diisocyanate or 4,4'-methylene double (ring) An alicyclic diisocyanate compound such as hexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate or 1,3-(isocyanatomethyl)cyclohexane; A diisocyanate compound or the like which is a reaction product of a diol and a diisocyanate, such as an addition product of 3-butanediol 1 mole and toluene diisocyanate 2 mole.

2) diol compound

The diol compound represented by the above formula (5) is broadly exemplified by a polyether diol compound, a polyester diol compound, a polycarbonate diol compound, and the like.

Here, a method of introducing an unsaturated group into a side chain of a polyurethane polymer uses a diol having an unsaturated group in a side chain in addition to the method described above. The compound is also preferred as a method for producing a raw material of a polyurethane polymer. Such a diol compound may be, for example, commercially available as trimethylolpropane monoallyl ether, or may be a halogenated diol compound, a triol compound, an amino diol compound, and an unsaturated group-containing carboxylic acid. A compound which is easily produced by the reaction of a hydrazine chloride, an isocyanate, an alcohol, an amine, a thiol or a halogenated alkyl compound. Specific examples of such compounds include the compounds shown below, but are not limited thereto.

Further, in the synthesis of the polyurethane in the present invention, a diol compound represented by the following formula (G) is used as a diol compound having an ethylenically unsaturated bonding group in the synthesis of a polyurethane. At least one of the resulting polyurethane resins.

In the above formula (G), R ¹ to R ³ each independently represent 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 )-, R ¹² represents a hydrogen atom or a monovalent organic group.

Moreover, the general formula (G) in the R ¹ ~ R ³ and X in the general formula R (1) is ¹ ~ R ³ and X have the same meaning, additional preferred aspects are also the same.

It is considered that by using a polyurethane resin derived from such a diol compound, it is possible to suppress the excessive molecular motion of the polymer main chain caused by the secondary alcohol having a large steric hindrance. The effect is to achieve an increase in the strength of the film of the layer.

Hereinafter, specific examples of the diol compound represented by the general formula (G) which can be preferably used for the synthesis of a specific polyurethane polymer are shown.

For example, in view of improving compatibility with other components in the polymerizable composition, improving storage stability, etc., the specific polyurethane resin used in the present invention can give the above-mentioned unsaturated group-containing diol. The diol compound other than the compound is copolymerized.

Examples of such a diol compound include the above polyether diol compound, polyester diol compound, and polycarbonate diol compound.

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

HO-(CH ₂ CH ₂ CH ₂ CH ₂ O) _c -H (9)

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

-CH ₂ CH ₂ -

Specific examples of the polyether diol compound represented by the above formula (7) and formula (8) include the following.

That is, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, and six ethylene Glycol, heptaethylene glycol, octaethylene glycol, di-1,2-propanediol, tri-1,2-propanediol, tetra-1,2-propanediol, hexa-1,2-propanediol, bis-1,3 -propylene glycol, tri-1,3-propanediol, tetra-1,3-propanediol, di-1,3-butanediol, tri-1,3-butanediol, hexa-1,3-butanediol, weight Polyethylene glycol having an average molecular weight of 1,000, polyethylene glycol having a weight average molecular weight of 1,500, polyethylene glycol having a weight average molecular weight of 2000, polyethylene glycol having a weight average molecular weight of 3,000, and a polycondensation having a weight average molecular weight of 7,500. Ethylene glycol, polypropylene glycol having a weight average molecular weight of 400, polypropylene glycol having a weight average molecular weight of 700, polypropylene glycol having a weight average molecular weight of 1,000, polypropylene glycol having a weight average molecular weight of 2000, polypropylene glycol having a weight average molecular weight of 3,000, and weight A polypropylene glycol having an average molecular weight of 4,000 or the like.

Specific examples of the polyether diol compound represented by the above formula (9) include the following.

That is, (trade name) manufactured by Sanyo Chemical Industry Co., Ltd. (trade name) PTMG650, PTMG1000, PTMG2000, PTMG3000, and the like.

Specific examples of the polyether diol compound represented by the above formula (10) include the following.

That is, Sanko Chemical Industry Co., Ltd. (trade name) Newpol PE-61, Newpol PE-62, Newpol PE-64, Newpol PE-68, Newpol PE-71, Newpol PE-74, Newpol PE-75, Newpol PE-78, Newpol PE-108, Newpol PE-128, Newpol PE-61, etc.

Specific examples of the polyether diol compound represented by the above formula (11) include the following.

That is, Sanpo Chemical Industry Co., Ltd. (trade name) Newpol BPE-20, Newpol BPE-20F, Newpol BPE-20NK, Newpol BPE-20T, Newpol BPE-20G, Newpol BPE-40, Newpol BPE-60, Newpol BPE-100, Newpol BPE-180, Newpol BPE-2P, Newpol BPE-23P, Newpol BPE-3P, Newpol BPE-5P, and the like.

Specific examples of the random copolymer of ethylene oxide and propylene oxide having a hydroxyl group at the terminal are as follows.

That is, Sanko Chemical Industry Co., Ltd. (trade name) Newpol 50HB-100, Newpol 50HB-260, Newpol 50HB-400, Newpol 50HB-660, Newpol 50HB-2000, Newpol 50HB-5100, etc.

The polyester diol compound may, for example, be a compound represented by the formula (12) or the formula (13).

In the formulae (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 hydrocarbon group. Preferably, L ² to L ⁴ represent an alkylene group, an alkenyl group, an alkynyl group, an extended aryl group, and L ⁵ represents an alkylene group. Further, L ² to L ⁵ may also have other functional groups which do not react with an isocyanate group, such as an ether, a carbonyl group, an ester, a cyano group, an olefin, a urethane, a guanamine, a ureido group or a halogen atom. . Each of n1 and n2 is an integer of 2 or more, and preferably an integer of 2 to 100.

The polycarbonate diol compound has 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 alkyl group, an alkenyl group, an alkynyl group or an extended aryl group. Further, other functional groups which do not react with the isocyanate group may be present in L ⁶ , such as an ether, a carbonyl group, an ester, a cyano group, an olefin, a urethane, a guanamine, a ureido group or a halogen atom. N3 is an integer of 2 or more, and preferably represents an integer of 2 to 100.

The diol compound represented by the above formula (12), formula (13) or formula (14) specifically includes the following (exemplified compound No. 1) to (exemplary compound No. 18). In the specific example, n represents an integer of 2 or more.

Further, in the case of synthesizing a specific polyurethane polymer, in addition to the above diol compound, a diol compound having a substituent which does not react with an isocyanate group may be used in combination. Such a diol compound includes, for example, those shown below.

HO-L ⁷ -O-CO-L ⁸ -CO-OL ⁷ -OH (15)

HO-L ⁸ -CO-OL ⁷ -OH (16)

In the formulae (15) and (16), L ⁷ and L ⁸ may be the same or different, and each of them may have a substituent (for example, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, or the like). a divalent aliphatic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group of each group such as a halogen atom such as F, -Cl, -Br or -I. Optionally, also to L ^7, L ⁸ having other functional group not reacting with an isocyanate group, such as carbonyl group, an ester group, a urethane group, an acyl group, a ureido group. Further, a ring may be formed by L ⁷ and L ⁸ .

Further, when a specific polyurethane polymer is synthesized, a diol compound having a carboxyl group may be used in combination in addition to the above diol compound.

Such a diol compound includes, for example, those represented by the following formulas (17) to (19).

In the formulae (17) to (19), R ¹⁵ represents a hydrogen atom and may have a substituent (for example, a halogen atom such as a cyano group, a nitro group, a -F, -Cl, -Br, or -I, -CONH ₂ , COOR ¹⁶ , -OR ¹⁶ , -NHCONHR ¹⁶ , -NHCOOR 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) The alkyl group, the aralkyl group, the aryl group, the alkoxy group and the aryloxy group of the group preferably represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an aryl group having 6 to 15 carbon atoms. . L ⁹ , L ¹⁰ and L ¹¹ may be the same or different, and represent a single bond, which may have a substituent (for example, preferably an alkyl group, an aralkyl group, an aryl group, an alkoxy group or a halogen group). The valence aliphatic or aromatic hydrocarbon group preferably represents an alkylene group having 1 to 20 carbon atoms and an extended aryl group having 6 to 15 carbon atoms, and preferably represents an alkylene group having 1 to 8 carbon atoms. base. Further, other functional groups which do not react with an isocyanate group, such as a carbonyl group, an ester, a urethane, a guanamine, a urea, or an ether group, may be further contained in L ⁹ to L ¹¹ as needed. Further, a ring may be formed by two or three 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.

The diol compound having a carboxyl group represented by the above formulas (17) to (19) specifically includes the following.

Namely, 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.

By having such a carboxyl group, it is preferable to impart characteristics such as hydrogen-bonding and alkali solubility to the polyurethane polymer. More specific The polyurethane polymer having an ethylenically unsaturated bonding group in the above side chain is a polymer further having a carboxyl group in a side chain, and more specifically, having a mechano group of 0.3 meq/g or more. A polyurethane urethane polymer having an ethylenically unsaturated bonding group and having a carboxyl group of 0.4 meq/g or more in a side chain can be preferably used as the binder polymer of the present invention.

In addition, in the case of synthesizing a specific polyurethane polymer, in addition to the above-mentioned diol, a tetracarboxylic dianhydride represented by the following formulas (20) to (22) may be opened by a diol compound in combination. a compound.

In the formula (20) to the formula (22), L ¹² represents a single bond and may have a substituent (for example, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, a halogeno group, an ester group, an decylamine group). The divalent aliphatic or aromatic hydrocarbon group, -CO-, -SO-, -SO ₂ -, -O- or S- of each group) preferably represents a single bond and has 1 to 15 carbon atoms. A divalent aliphatic hydrocarbon group, -CO-, -SO ₂ -, -O- or S-. 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 halogen group, and preferably represents a hydrogen atom and an alkyl group having 1 to 8 carbon atoms. The carbon number is 6 to 15 aryl groups, and the carbon number is 1 to 8 alkoxy groups or halogen groups. Further, two of L ¹² , R ¹⁷ and R ¹⁸ may be bonded to each other 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 halogen group, preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a carbon number of 6 ~15 aryl groups. Further, two of L ¹² , R19 and R20 may be bonded to each other 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 is an aromatic ring having 6 to 18 carbon atoms.

The compound represented by the above formula (20), formula (21) or formula (22) specifically includes the following.

That is, pyromellitic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic 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'-(alkylphosphonium bismuth) Phenyl)-bis(iminocarbonyl)]diphthalic dianhydride, adduct of hydroquinone diacetate and trimellitic anhydride, diethylaminodiamine and trimellitic anhydride Adducts and other aromatic tetracarboxylic dianhydrides; 5-(2,5-dioxotetrahydrofuranyl)-3-methyl 3-cyclohexene-1,2-dicarboxylic anhydride (manufactured by Dainippon Ink Chemical Industry Co., Ltd., Epiclon B-4400), 1,2,3,4-cyclopentane tetracarboxylic acid Alicyclic tetracarboxylic dianhydride such as acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride or tetrahydrofuran tetracarboxylic dianhydride; 1,2,3,4-butane tetracarboxylic acid An aliphatic tetracarboxylic dianhydride such as dianhydride or 1,2,4,5-pentanetetracarboxylic dianhydride.

A method of introducing a compound obtained by ring-opening the tetracarboxylic dianhydride with a diol compound into a polyurethane polymer is, for example, the following method.

a) A method of reacting a compound having an alcohol which is obtained by ring-opening a tetracarboxylic dianhydride with a diol compound and a diisocyanate compound.

b) A method of reacting an alcohol-based urethane compound obtained by reacting a diisocyanate compound under an excess of a diol compound with tetracarboxylic dianhydride.

Further, the diol compound used in the ring opening reaction at this time specifically includes the following.

That is, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butanediol, 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, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, bisphenol F Ethylene oxide adduct, propylene oxide adduct of bisphenol F, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, hydroquinone II Hydroxyethyl ether, p-xylene glycol, dihydroxyethyl hydrazine, bis(2-hydroxyethyl)-2,4-toluenedicarbamate, 2,4-toluene-bis(2-hydroxyethyl) Aminoguanidine Amine), bis(2-hydroxyethyl)-m-xylylenedicarbamate, bis(2-hydroxyethyl)isophthalate, and the like.

The specific polyurethane polymer which can be used in the present invention is synthesized by adding an activity corresponding to the reactivity of each of the above-mentioned diisocyanate compound and diol compound to an aprotic solvent. The catalyst is known and heated. The molar ratio (M _a :M _b ) of the diisocyanate and the diol compound used in the synthesis is preferably from 1:1 to 1.2:1, and is treated by an alcohol or an amine to have no residual residue. The form of the cyanate group synthesizes a product of desired physical properties such as molecular weight or viscosity.

The introduction amount of the ethylenically unsaturated bond contained in the specific polyurethane polymer of the present invention is preferably an equivalent of 0.3 meq/g or more of ethylenically unsaturated bonds in the side chain. Further, it is preferred to contain an ethylenically unsaturated bonding group of 0.35 meq/g to 1.50 meq/g.

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

In the present invention, a styrene-based polymer having an ethylenically unsaturated bond in a side chain (hereinafter sometimes referred to as "styrene-based polymer") is also preferable, and preferably has a formula represented by the following formula (23) At least one of a styrene double bond (styrene and an α-methylstyrene double bond) and a vinyl pyridinium group represented by the following formula (24).

In the formula (23), R ²¹ represents a hydrogen atom or a methyl group. R ²² represents any atom or group of atoms which may be substituted. k represents an integer from 0 to 4.

In addition, the styrene double bond represented by the formula (23) is bonded to the polymer main chain via a single bond or a linking group containing an arbitrary atom or atomic group, and the bonding method is not particularly limited.

Hereinafter, preferred examples of the repeating unit of the polymer compound having a functional group represented by the formula (23) are shown, but the present invention is not limited to these examples.

In the formula (24), R ²³ represents a hydrogen atom or a methyl group. R ²⁴ represents any atom or group of atoms which may be substituted. m represents an integer from 0 to 4. A ^- represents an anion. Further, the pyridinium ring may also be in the form of a benzopyridinium condensed with a benzene ring as a substituent, and in this case, a quinolinyl group and an isoquinolinyl group are contained.

In addition, the vinyl pyridinium group represented by the formula (24) is bonded to the polymer main chain via a single bond or a linking group containing an arbitrary atom or an atomic group, and the bonding method is not particularly limited.

Hereinafter, preferred examples of the repeating unit of the polymer compound having a functional group represented by the general formula (24) are shown, but the present invention is not limited to these examples.

One of the methods for synthesizing the styrene-based polymer is a functional group represented by the above formula (23) or formula (24) and copolymerizable with other copolymerized components by a known copolymerization method. A method in which monomers of a functional group are copolymerized with each other. Here, the styrenic polymer may have the general formula (23) and the general formula (24) The homopolymer of only one of any of the functional groups represented may be a copolymer having two or more of any one or two of the functional groups.

Further, it may be a copolymer with another copolymerizable monomer which does not contain such a functional group. In the case of the other copolymerizable monomer in this case, for example, in order to impart solubility to the alkaline aqueous solution to the polymer, it is preferred to select a monomer having a carboxyl group, and examples thereof include acrylic acid, methacrylic acid, and 2-carboxyethyl acrylate. Examples of 2-carboxyethyl methacrylate, crotonic acid, maleic acid, fumaric acid, monoalkyl maleate, monoalkyl fumarate, 4-carboxystyrene, and the like.

It is also preferred to carry out the following steps: introducing a monomer component into the copolymer in addition to the monomer having a carboxyl group, and synthesizing and using it as a (multicomponent) copolymer. Regarding the monomer which can be incorporated into the copolymer in this case, the following monomers can be suitably used as the copolymerizable monomer: styrene, 4-methylstyrene, 4-hydroxystyrene, 4-ethenyloxy group Styrene derivatives such as styrene, 4-carboxystyrene, 4-aminostyrene, chloromethylstyrene, 4-methoxystyrene, vinylphosphonic acid, vinylsulfonic acid and its salts, styrene Sulfonic acid and its salt, 4-vinylpyridine, 2-vinylpyridine, N-vinylimidazole, N-vinylcarbazole, 4-vinylbenzyltrimethylammonium chloride, N-vinylimidazole Terpolymer of methyl chloride, -4-chlorobenzylpyridinium chloride, acrylonitrile, methacrylonitrile, phenyl maleimide, hydroxyphenyl maleimide, vinyl acetate, chlorine Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, vinyl benzoate, vinyl ethers such as methyl vinyl ether and butyl vinyl ether, N-vinyl Various monomers such as pyrrolidone, acryloylmorpholine, vinyl chloride, vinylidene chloride, allyl alcohol, vinyl trimethoxydecane.

In the case where the copolymer as described above is used as the styrene-based 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 total copolymer composition It is preferably 20% by mass or more, and more preferably 40% by mass or more. Within this range, the present invention is excellent in effect and forms a high-sensitivity relationship.

The molecular weight of the styrene-based polymer is preferably in the range of 10,000 to 300,000, more preferably in the range of 15,000 to 200,000, and most preferably in the range of 20,000 to 150,000.

For the polymer having an ethylenic unsaturated bond in the other side chain, the novolac polymer having an ethylenically unsaturated group in the side chain is exemplified by the polymer described in Japanese Laid-Open Patent Publication No. Hei 9-269596. A polymer obtained by introducing an ethylenically unsaturated bond into a side chain by the method described in JP-A-2002-62648.

In addition, examples of the acetal polymer having an ethylenically unsaturated bond in the side chain include a polymer described in JP-A-2002-162741.

Further, examples of the polyamine-based polymer having an ethylenically unsaturated bond in the side chain include a polymer described in Japanese Patent Application Laid-Open No. 2003-321022, or a polyamine polymer cited therein. The method described in JP-A-2002-62648 discloses a polymer obtained by introducing an ethylenically unsaturated bond into a side chain.

The polyimine polymer having an ethylenic unsaturated bond in the side chain is exemplified by the polymer described in Japanese Patent Application Laid-Open No. 2003-339785, or the polyimine polymer cited therein. Opened the 2002-62648 bulletin The method described in the above is a polymer obtained by introducing an ethylenically unsaturated bond into a side chain.

<<C: Compound having an epoxy group or an oxetanyl group>>

A third preferred embodiment of the present invention is a form containing a compound having an epoxy group or an oxetanyl group as a polymerizable compound. The compound having an epoxy group or an oxetanyl group specifically has a polymer having an epoxy group in a side chain and a polymerizable monomer or oligomer having two or more epoxy groups in the molecule. Listed: bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, aliphatic epoxy resin, and the like.

These compounds can be used as a commercial product, and can also be obtained by introducing an epoxy group to a side chain of a polymer.

As a commercial item, for example, bisphenol A type epoxy resin is JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (The above is manufactured by Japan Epoxy Resin Co., Ltd.), Abby Clones ( EPICLON) 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (above, DIC), etc.; bisphenol F epoxy resin is JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above is made by Japan Epoxy Resin Co., Ltd.), Epiclon 830, EPICLON 835 (above is Di Aisheng (DIC) Co., Ltd.) Manufactured), LCE-21, RE-602S (the above is manufactured by Nippon Kayaku Co., Ltd.), etc.; phenol novolac type epoxy resin is JER152, JER154, JER157S70, JER157S65 (the above is manufactured by Japan Epoxy Resin Co., Ltd.) , EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (above), etc.; cresol novolac epoxy resin is Epiclon N -660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N -690, Epiclon (EPICLON) N-695 (above is manufactured by Di Aisheng (DIC) Co., Ltd.), EOCN-1020 (above is made by Nippon Chemical Co., Ltd.), etc., aliphatic epoxy resin is Eddie ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S (above ADEKA), Siro Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE 3150, EPOLEAD PB 3600, EPOLEAD ) PB 4700 (above produced by Daicel Chemical Industry Co., Ltd.), Denacol EX-212L, Denacol EX-214L, and Denacol EX- 216L, Denacol EX-321L, Denacol EX-850L ( On to Nagase Kasei (Nagase Chemtex) (shares)) and the like. In addition, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, Adeco resin (ADEKA) RESIN)EP-4011S (above is made by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above is Edico ( ADEKA) (manufacturing), JER1031S (Japanese epoxy resin) Made) and so on.

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 above molecule may be used: arronoxaline ( Aron Oxetane) OXT-121, Aron Oxetane OXT-221, Aron Oxetane OX-SQ, Aron Oxetane PNOX (Aron Oxetane) The above is manufactured by East Asia Synthetic Co., Ltd.).

In the case where the above group is introduced into the polymer side chain to carry out the synthesis, the introduction reaction can be carried out, for example, by subjecting a tertiary amine such as triethylamine or benzylmethylamine to dodecyl chloride. a tetrabasic ammonium salt such as trimethylammonium chloride, tetramethylammonium chloride or tetraethylammonium chloride, pyridine or triphenylphosphine as a catalyst, and reacted in an organic solvent at a reaction temperature of 50 ° C to 150 ° C Hours to tens of hours. The introduction amount of the alicyclic epoxy unsaturated compound is preferably such that the acid value of the obtained polymer satisfies 5 KOH. Mg/g~200KOH. The manner of the range of mg/g is controlled. Further, the molecular weight is represented by a weight average molecular weight, preferably from 500 to 5,000,000, more preferably from 1,000 to 500,000.

As the epoxy-unsaturated compound, a glycidyl group such as glycidyl (meth)acrylate or allyl glycidyl ether may be used as the epoxy group, and an unsaturated compound having an alicyclic epoxy group is preferred. Such a compound can be exemplified by the following compounds, for example.

The details of the use of the polymerizable compound, such as the structure, the use alone or in combination, and the amount of addition, can be arbitrarily set according to the final performance design of the near-infrared absorbing composition. For example, from the viewpoint of sensitivity, it is preferred that the structure has a large content of unsaturated groups per molecule, and in many cases, it is preferably a bifunctional or higher. In addition, from the viewpoint of improving the strength of the near-infrared cut filter, it is preferable to use a trifunctional or higher functional group, and further, the functional group is different and the polymerizable group is different (for example, acrylate, methacrylate, or styrene). A method of adjusting both sensitivity and strength by a compound or a vinyl ether compound is also effective. In addition, the compatibility and dispersibility of other components (for example, metal oxide, dye, polymerization initiator) contained in the near-infrared absorbing composition, selection and use of the polymerizable compound The method is also an important factor. For example, it is sometimes possible to improve the compatibility by using a low-purity compound or a combination of two or more. Moreover, a specific structure can also be selected from the viewpoint of improving the adhesion to a hard surface such as a support.

The amount of the polymerizable compound added to the composition of the present invention is preferably from 1% by mass to 80% by mass, more preferably from 15% by mass to 70% by mass, based on the total solid content other than the solvent. It is added in the range of 20% by mass to 60% by mass.

The polymerizable compound may be used alone or in combination of two or more kinds. In the case of two or more types, the total amount is in the above range.

<adhesive polymer>

In the present invention, in order to improve the film properties and the like, a binder polymer may be further contained in addition to the above polymerizable compound. As the binder polymer, an alkali-soluble resin can be preferably used. By containing an alkali-soluble resin, it is effective in the improvement of heat resistance, etc., or fine adjustment of coating suitability.

The alkali-soluble resin can be appropriately selected from the following alkali-soluble resins, which are linear organic high-molecular polymers, and are in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It has at least one group that promotes alkali solubility. From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polyoxyalkylene resin, an acrylic resin, an acrylamide resin, or an acrylic acid/acrylamide copolymer resin is preferred in terms of controlling developability. In particular, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin is preferable.

Examples of the group which promotes alkali solubility (hereinafter also referred to as an acid group) include, for example: The carboxyl group, the phosphoric acid group, the sulfonic acid group, the phenolic hydroxyl group and the like are preferably soluble in an organic solvent and can be developed by using a weakly basic aqueous solution, and (meth)acrylic acid is particularly preferred. These acid groups may be used alone or in combination of two or more.

The monomer which can provide an acid group after the above-mentioned polymerization, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate or a monomer having an epoxy group such as glycidyl (meth)acrylate, A monomer having an isocyanate group or the like such as 2-isocyanatoethyl (meth)acrylate. These monomers for introducing an acid group may be used alone or in combination of two or more. In order to introduce an acid group into the 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 "a monomer for introducing an acid group") The polymerization may be carried out as a monomer component. In the case where a monomer capable of imparting an acid group after polymerization is introduced as a monomer component, it is necessary to carry out a treatment for imparting an acid group as described later after the polymerization.

When the alkali-soluble resin is produced, for example, a known method using a radical polymerization method can be applied. The polymerization conditions such as the temperature, the pressure, the type and amount of the radical initiator, and the kind of the solvent when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art, and the conditions can be determined experimentally. .

The linear organic high molecular polymer which can be used as the alkali-soluble resin is preferably a polymer having a carboxylic acid in a side chain, and examples thereof include a methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, and a butenoic acid copolymer. , an alkali-soluble phenol resin such as a maleic acid copolymer, a partially esterified maleic acid copolymer, a novolac type resin, or the like, and an acidic cellulose derivative having a carboxylic acid in a side chain, and an addition to a polymer having a hydroxyl group Anhydride is the only one. In particular, copolymerization of (meth)acrylic acid with other monomers copolymerizable therewith The material is also suitable as an alkali soluble resin. Examples of the other monomer copolymerizable with (meth)acrylic acid include alkyl (meth)acrylate, aryl (meth)acrylate, and a vinyl compound. Examples of the alkyl (meth)acrylate and the aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. Ester, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate , (methyl) methacrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc.; examples of the vinyl compound: styrene, α-methyl styrene, vinyl toluene, methacrylic acid Glycidyl ester, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, etc., Japanese Patent Laid-Open No. 10-300922 N-phenylmaleimide, N-cyclohexylmaleimide, or the like, which is a N-substituted maleimide monomer described in the publication. Further, these other monomers copolymerizable with (meth)acrylic acid may be used alone or in combination of two or more.

The alkali-soluble resin preferably further contains the following polymer (a) as the polymer component (A) (the polymer component (A) is an essential component), and the above polymer (a) is required to have the following formula (ED) The monomer component of the compound (hereinafter sometimes referred to as "ether dimer") is polymerized.

(In the formula (ED), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent). Thereby, the composition of the present invention can form a cured coating film which is extremely excellent in heat resistance and transparency. In the above formula (1), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ^{2 in} the above-mentioned ether dimer is not particularly limited, and examples thereof include a methyl group and an ethyl group. a linear or branched alkyl group such as n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-pentyl, stearyl, lauryl or 2-ethylhexyl; benzene An aryl group; an alicyclic group such as a cyclohexyl group, a tert-butylcyclohexyl group, a dicyclopentadienyl group, a tricyclodecanyl group, an isodecyl group, an adamantyl group or a 2-methyl-2-adamantyl group; An alkyl group substituted with an alkoxy group such as 1-methoxyethyl or 1-ethoxyethyl; an alkyl group substituted with an aryl group such as a benzyl group; and the like. Among these, in particular, in terms of heat resistance, a substituent of a primary or secondary carbon which is not easily removed by acid or heat such as a methyl group, an ethyl group, a cyclohexyl group or a benzyl group is preferable.

Specific examples of the ether dimer include dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate (dimethyl-2,2'-[oxybis(methylene)). Bis-2-propenoate), diethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, di(n-propyl)-2,2'-[oxy double (methylene)]bis-2-acrylate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(n-butyl)-2 , 2'-[oxybis(methylene)]bis-2-acrylate, di(isobutyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, Bis(t-butyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, bis(third pentyl)-2,2'-[oxybis (methylene Base]] bis-2-acrylate, bis(stearyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, bis(lauryl)-2,2'- [oxybis(methylene)]bis-2-acrylate, di(2-ethylhexyl) -2,2'-[oxybis(methylene)]bis-2-acrylate, bis(1-methoxyethyl)-2,2'-[oxybis(methylene) Bis-2-acrylate, bis(1-ethoxyethyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, dibenzyl-2,2'- [oxybis(methylene)]bis-2-acrylate, diphenyl-2,2'-[oxybis(methylene)]bis-2-acrylate, dicyclohexyl-2,2 '-[oxybis(methylene)]bis-2-acrylate, bis(t-butylcyclohexyl)-2,2'-[oxybis(methylene)]bis-2-acrylate , bis(dicyclopentadienyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, bis(tricycloindenyl)-2,2'-[oxy double (methylene)] bis-2-acrylate, bis(isoindenyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, diamantyl-2,2 '-[Oxobis(methylene)]bis-2-acrylate, bis(2-methyl-2-adamantyl)-2,2'-[oxybis(methylene)]-di- 2-acrylate and the like. Particularly preferred among these are dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, diethyl-2,2'-[oxybis(methylene) )] bis-2-acrylate, dicyclohexyl-2,2'-[oxybis(methylene)]bis-2-acrylate, dibenzyl-2,2'-[oxy double (Asia Methyl)] bis-2-acrylate. These ether dimers may be used alone or in combination of two or more. The structure derived from the compound represented by the above formula (ED) may also copolymerize other monomers.

In the present invention, the structural unit derived from the ether dimer is preferably from 1 mol% to 50 mol%, more preferably from 1 mol% to 20 mol%.

Other monomers may also be copolymerized with the ether dimer.

Examples of the other monomer copolymerizable with the ether dimer include a monomer for introducing an acid group, a monomer for introducing a radical polymerizable double bond, a monomer for introducing an epoxy group, and Other copolymerizable monomers other than these. These monomers may be used alone or in combination of two or more.

Examples of the monomer for introducing an acid group include a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid, a monomer having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide, and maleic anhydride. A monomer having a carboxylic anhydride group such as itaconic anhydride. Among these, (meth)acrylic acid is particularly preferred.

Further, the monomer for introducing an acid group may be a monomer which can impart an acid group after polymerization, and examples thereof include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, and (meth) A monomer having an epoxy group such as a glycidyl acrylate or a monomer having an isocyanate group such as 2-isocyanatoethyl (meth)acrylate. In the case of using a monomer which can impart an acid group after polymerization, it is necessary to carry out a treatment for imparting an acid group after polymerization. The treatment for imparting an acid group after the polymerization differs depending on the type of the monomer, and examples thereof include the following treatments. 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 or maleic anhydride can be mentioned. In the case of using a monomer having an epoxy group, for example, a compound having an amine group and an acid group such as N-methylaminobenzoic acid or N-methylaminophenol may be added, or for example, The addition of an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride or maleic anhydride to a hydroxyl group formed by adding an acid such as (meth)acrylic acid is carried out. 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 a polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) is contained in a monomer containing an acid group, the content ratio thereof is not particularly limited, and among all the monomer components, It is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 60% by mass.

Examples of the monomer to introduce a radical polymerizable double bond include a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid; and a monomer having a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride; A monomer having an epoxy group such as glycidyl acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, o- (or m- or m-)-vinyl benzyl glycidyl ether or the like. When a monomer for introducing a radically polymerizable double bond is used, it is necessary to carry out a treatment for imparting a radical polymerizable double bond after polymerization. The treatment for imparting a radically polymerizable double bond after the polymerization differs depending on the type of the monomer which can impart a radical polymerizable double bond, and examples thereof include the following treatments. When a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid is used, an addition of glycidyl (meth)acrylate or a 3,4-epoxycyclohexyl (meth)acrylate may be mentioned. Treatment of a compound having an epoxy group and a radically polymerizable double bond such as a methyl ester, o- (or m- or p-) vinylbenzyl glycidyl ether. When a monomer having a carboxylic anhydride group such as maleic anhydride or itaconic anhydride is used, a compound having a hydroxyl group and a radical polymerizable double bond such as 2-hydroxyethyl (meth)acrylate may be added. Processing. If using glycidyl (meth)acrylate, -3,4-epoxycyclohexylmethyl (meth)acrylate, o- (or m- or p-) vinylbenzyl glycidyl ether, etc. In the case of a monomer, a treatment of a compound having an acid group and a radical polymerizable double bond such as (meth)acrylic acid may be mentioned.

In the case where 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 thereof is not particularly limited. The body component is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 60% by 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 chloride. Glycidyl ether and the like.

In the case where 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 thereof is not particularly limited, and is contained in all the monomer components. It is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 60% by mass.

Examples of other copolymerizable monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylic acid. N-butyl ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, methyl 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, (methyl) (meth) acrylate such as benzyl acrylate or 2-hydroxyethyl (meth) acrylate; aromatic vinyl compound such as styrene, vinyl toluene or α-methyl styrene; N-phenyl mala N-substituted maleimide such as imine, N-cyclohexylmaleimide; butadiene or substituted butadiene compound such as butadiene or isoprene; ethylene, propylene, vinyl chloride, propylene Ethylene or a substituted vinyl compound such as a nitrile; a vinyl ester such as vinyl acetate or 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 thereof is not particularly limited, but is preferably 95% by mass or less. More preferably, it is 85% by mass or less.

Polymerization of a monomer component containing a compound represented by the general formula (ED) The weight average molecular weight of the polymer is not particularly limited, and is preferably from 2,000 to 200,000, more preferably from 2,000 to 200,000, from the viewpoint of the viscosity of the coloring radiation-sensitive composition and the heat resistance of the coating film formed of the composition. 5000~100000, and then 5000~20000.

In the case where the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) has an acid group, the acid value is preferably from 30 mgKOH/g to 500 mgKOH/g, more preferably 50 mgKOH/ G~400mgKOH/g is preferred.

A polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) can be easily obtained by polymerizing the above monomer having at least an essential ether dimer. At this time, the cyclization reaction of the ether dimer is carried out at the same time as the polymerization to form a tetrahydropyran ring structure.

The polymerization method to be used in 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 employed, and it is particularly preferred to use a solution polymerization method. Specifically, for example, a polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) can be synthesized according to the method for synthesizing the polymer (a) described in JP-A-2004-300204. .

Hereinafter, an exemplary compound of a polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) is shown, but the present invention is not limited to these compounds. The composition ratio of the exemplified compounds shown below is mol% (% by mole).

In the present invention, dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate (hereinafter referred to as "DM") or benzyl methacrylate (hereinafter referred to as dimethyl methacrylate) is preferred. Copolymerization of "BzMA"), methyl methacrylate (hereinafter referred to as "MMA"), methacrylic acid (hereinafter referred to as "MAA"), and glycidyl methacrylate (hereinafter referred to as "GMA") The resulting polymer. Youjia is DM: BzMA: MMA: MAA: GMA has a molar ratio of 5~15:40~50:5~15:5~15:20~30. It is preferred that 95% by mass or more of the components constituting the copolymer used in the present invention are the components. Further, the weight average molecular weight of the polymer is preferably from 9000 to 20,000.

In the present invention, an alkali-soluble phenol resin can also be preferably used. Alkali solubility Examples of the phenol resin include a novolak resin and a vinyl polymer.

The novolac resin is, for example, one obtained by condensing a phenol and an aldehyde in the presence of an acid catalyst. Examples of the phenols include phenol, cresol, ethyl phenol, butyl phenol, xylenol, phenylphenol, catechol, resorcinol, and benzenetriol. (pyrogallol), naphthol (naphthol) or bisphenol A.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde or benzaldehyde.

The above phenols and aldehydes may be used alone or in combination of two or more.

Specific examples of the novolak resin include m-cresol, p-cresol or a condensation product of such a mixture with formalin.

The above novolak resin can also be adjusted to have a molecular weight distribution by means of fractionation or the like. Further, a low molecular weight component having a phenolic hydroxyl group such as bisphenol C or bisphenol A may be mixed into the novolak resin.

The alkali-soluble resin is particularly preferably a multicomponent copolymer comprising a benzyl (meth)acrylate/(meth)acrylic acid copolymer or a benzyl (meth)acrylate/(meth)acrylic acid/other monomer. Further, the copolymerization of 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer described in JP-A-7-140654 Benzyl acrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, methacrylic acid -2-Hydroxyethyl/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methacryl Benzyl methacrylate / methacrylic acid copolymer and the like.

The acid value of the alkali-soluble resin is preferably from 30 mgKOH/g to 200 mgKOH/g, more preferably from 50 mgKOH/g to 150 mgKOH/g, most preferably from 70 mgKOH/g to 120 mgKOH/g.

Further, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably from 2,000 to 50,000, more preferably from 5,000 to 30,000, most preferably from 7,000 to 20,000.

The content of the binder polymer of the present invention is preferably from 1% by mass to 80% by mass, more preferably from 10% by mass to 70% by mass, even more preferably from 20% by mass to 60% by mass, based on the total solid content of the composition. .

<solvent>

The composition of the present invention preferably contains a solvent. The solvent may be one type or two or more types. When two or more types are used, the total amount is in the above range. The solvent is preferably contained in a proportion of 10% by mass to 65% by mass based on the composition, more preferably 20% by mass to 65% by mass based on the composition, and particularly preferably 30% by mass to 655% by mass. % solvent.

The solvent to be used in the present invention is not particularly limited, and may be appropriately selected according to the purpose, as long as the components of the composition of the present invention are uniformly dissolved or dispersed. For example, as an alcohol, for example, Methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, n-hexanol, etc.; and as ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, Cyclopentanone, 2-heptanone, 3-heptanone, etc.; Examples of the esters include ethyl acetate, n-butyl acetate, n-amyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, ethyl propionate, butyl propionate, butyric acid. Isopropyl ester, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, dimethyl phthalate, ethyl benzoate, methyl sulfate, alkyl oxyacetate (eg oxyacetic acid) Methyl ester, ethyl oxyacetate, butyl oxyacetate (such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate) Etc)), 3-oxopropionic acid alkyl esters (such as methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (such as methyl 3-methoxypropionate, 3-methoxy Ethyl propyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-oxopropionate (for example, methyl 2-oxypropionate, Ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-oxy-2-methylpropanoate and 2- Ethyl 2-methylpropionate (eg methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, acetone Ethyl acetate, propyl pyruvate, methyl acetate methyl acetate, ethyl acetate ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutanoate, etc.; and, for example, diethylene glycol as an ether Dimethyl ether, tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate And, as aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene, etc.; And as halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, dichloromethane, monochlorobenzene, etc.; and dimethylformamide, dimethylethyl Indoleamine, dimethyl hydrazine, cyclobutyl hydrazine and the like. These solvents may be used alone or in combination of two or more. In this case, it is more preferably a mixed solution selected from two or more of the following solvents: methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl cellosolve B. Acid ester, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl card Alcohol acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.

<Polymerization initiator>

The composition of the present invention may also contain a polymerization initiator. The polymerization initiator may be used alone or in combination of two or more. In the case of two or more types, the total amount is in the above range. It is preferably from 0.01% by mass to 30% by mass, more preferably from 0.1% by mass to 20% by mass, even more preferably from 0.1% by mass to 15% by mass.

The polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound by either light or heat, and may be appropriately selected depending on the intended purpose, and is preferably a photopolymerizable compound. In the case where polymerization is initiated by light, it is preferred to have a sensitivity to ultraviolet light to visible light.

Further, in the case where polymerization is initiated by heat, a polymerization initiator which decomposes at 150 ° C to 250 ° C is preferred.

The polymerization initiator which can be used in the present invention preferably has at least an aromatic Examples of the compound of the group include a mercaptophosphine compound, an acetophenone compound, an α-aminoketone compound, a benzophenone compound, a benzoin ether compound, a ketal derivative compound, and a thioxanthone compound. Anthraquinone compound, hexaarylbiimidazole compound, halomethyl compound, azo compound, organic peroxide, diazonium compound, hydrazine compound, hydrazine compound, azinium compound, benzoin An oxime salt compound such as an ether compound, a ketal derivative compound or a metallocene compound, an organic boron salt compound or a diterpene compound.

From the viewpoint of sensitivity, an anthracene compound, an acetophenone-based compound, an α-aminoketone compound, a trihalomethyl compound, a hexaarylbiimidazole compound, and a thiol compound are preferable.

Examples of the polymerization initiators suitable for the present invention are listed below, but the present invention is not limited by the examples.

Specific examples of the acetophenone-based compound include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, and 2-hydroxy-2-methyl-1-phenyl-propane. 1-ketone, p-dimethylaminoacetophenone, 4'-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-one, 2-benzyl -2-Dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-tolyl-2-dimethylamino-1-(4-morpholinyl) Phenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylacetone-1, 2-methyl-1-(4-methylthio) Phenyl)-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-(dimethyl Amino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and 2-methyl- 1-(4-Methylthiophenyl)-2-morpholinylpropan-1-one and the like.

More preferably, the trihalomethyl compound may be a s-triazine derivative in which at least one monohalogen-substituted methyl group, dihalo-substituted methyl group or trihalogen-substituted methyl group is bonded to a s-triazine ring, specifically, for example, There may be mentioned 2,4,6-tris(monochloromethyl)s-triazine, 2,4,6-tris(dichloromethyl)s-triazine, 2,4,6-tris(trichloromethyl) Homotriazine, 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-(pair Methoxyphenyl)-4,6-bis(trichloromethyl)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-(p-isopropoxystyryl)-4,6-bis(trichloromethyl)s-triazine, 2-(p-tolyl)-4,6 - bis(trichloromethyl)s-triazine, 2-(4-naphthyloxynaphthyl)-4,6-bis(trichloromethane) a 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 or the like.

Examples of the hexaarylbiimidazole compound include various compounds described in the respective specifications, such as Japanese Patent Publication No. Hei. 6-29285, U.S. Patent No. 3,479,185, U.S. Patent No. 4,311,783, and U.S. Patent No. 4,622,286. , 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)-linked Azole, 2,2'-bis(o-o-o-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-nitrophenyl)- 4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2' - bis(o-trifluorophenyl)-4,4',5,5'-tetraphenylbiimidazole or the like.

Examples of ruthenium compounds include: Journal of the Chemical Society (JCS) Perkin II (1979) 1653-1660, Journal of the Chemical Society (JCS) Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, Journal of Applied Polymer Science (2012) pp. 725-pp.731 The compound described in JP-A-2000-66385, the compound described in JP-A-2000-80068, JP-A-2004-534797, and Iruka (BASF Japan) IRGACURE) OXE 01 (1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzylidene)), IRGACURE OXE 02 (ethyl ketone) , 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(0-ethylindenyl), 2-(ethylidene) Oxyimidomethyl)thioxanthene-9-one, and the like.

It is preferable to further preferably use a cyclic anthracene compound described in JP-A-2007-231000 and JP-A-2007-322744.

In addition, an antimony compound having a specific substituent disclosed in Japanese Laid-Open Patent Publication No. 2007-269779, or a ruthenium compound having a thioaryl group disclosed in Japanese Laid-Open Patent Publication No. 2009-191061 .

Specifically, the ruthenium compound is also preferably represented by the following formula (1). Compound. Further, it may be a ruthenium compound in which the N-O bond of ruthenium is (E), or a ruthenium compound in which the N-O bond of ruthenium is (Z), or a mixture of (E) and (Z).

(In the 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 the above R is preferably a monovalent non-metal atomic group. The monovalent non-metal atomic group may, for example, be an alkyl group, an aryl group, a decyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group or an arylthiocarbonyl group. Further, these groups may have one or more substituents. Further, the substituents described above may be further substituted with other substituents.

Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, a decyloxy group, a decyl group, an alkyl group, an aryl group and the like.

The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. Alkyl, isopropyl, isobutyl, t-butyl, tert-butyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, trifluoromethyl, 2-ethylhexyl, benzamidine Phenacy, 1-naphthylmethylmethyl, 2-naphthylmethylmethyl, 4-methylmercaptobenzylidenemethyl, 4-phenylmercaptobenzylidenemethyl, 4-dimethyl Aminobenzidine methyl, 4-cyanobenzoquinone , 4-methylbenzhydrylmethyl, 2-methylbenzimidylmethyl, 3-fluorobenzhydrylmethyl, 3-trifluoromethylbenzimidylmethyl and 3-nitrobenzhydrazide methyl.

The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and specific examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-fluorenyl group, and a 9-phenanthryl group. 1-indenyl, 5-fused tetraphenyl, 1-indenyl, 2-indenyl, 9-fluorenyl, terphenyl, quarterphenyl, o-tolyl , m-tolyl and p-tolyl, xylyl, ortho-alkenyl, m-cumenyl and p-cumenyl, 2,4,6-trityl, and pentalenyl , binaphthalenyl, trinaphthyl, tetranaphthyl, heptalenyl, biphenylenyl, dicyclopentyl (indacenyl), propyl [two ] fluoranthenyl, acenaphthylenyl, aceanthrylenyl, phenalenyl, fluorenyl, fluorenyl, hydrazino, triple fluorenyl, tetradecyl, Anthraquinolyl, phenanthryl, triphenylenyl, sulfhydryl, Chrysenyl, condensed tetraphenyl, pleiadenyl, picenyl, perylenyl, pentaphenyl, pentacenyl, tetraphenylenyl , hexaphenyl, hexaphenyl, rubicenyl, coronenyl, trinaphthylenyl, heptaphenyl, hexaphenyl, pyranthrenyl and ovalenyl ).

The fluorenyl group which may have a substituent is preferably a fluorenyl group having 2 to 20 carbon atoms, and specific examples thereof include an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, a trifluoroethyl fluorenyl group, a amyl group, a benzamidine group, and a group. Naphthylmethyl, 2-naphthylmethyl, 4-methylmercaptobenzyl, 4-phenylindenyl Benzyl fluorenyl, 4-dimethylaminobenzimidyl, 4-diethylaminobenzimidyl, 2-chlorobenzylidene, 2-methylbenzhydryl, 2-methoxy Benzobenzyl, 2-butoxybenzhydryl, 3-chlorobenzhydryl, 3-trifluoromethylbenzhydryl, 3-cyanobenzylidene, 3-nitrobyl Sulfhydryl, 4-fluorobenzhydryl, 4-cyanobenzylidene and 4-methoxybenzimidyl.

The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, and specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, and a hexyloxy group. A carbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethoxycarbonyl group.

Specific examples of the aryloxycarbonyl group which may have a substituent include a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylnonylphenoxycarbonyl group, and a 4-phenylmercaptophenoxy group. Carbonyl, 4-dimethylaminophenoxycarbonyl, 4-diethylaminophenoxycarbonyl, 2-chlorophenoxycarbonyl, 2-methylphenoxycarbonyl, 2-methoxyphenoxy Carbocarbonyl, 2-butoxyphenoxycarbonyl, 3-chlorophenoxycarbonyl, 3-trifluoromethylphenoxycarbonyl, 3-cyanophenoxycarbonyl, 3-nitrophenoxycarbonyl, 4-fluorophenoxycarbonyl, 4-cyanophenoxycarbonyl and 4-methoxyphenoxycarbonyl.

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.

Specific examples thereof include: thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthrenyl, furyl, pyranyl, isobenzofuranyl, benzopyrazine Chromenyl, Xanthenyl, phenoxathiinyl, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyridazinyl, isoindole Base, 3H-indenyl, fluorenyl, 1H-carbazolyl, fluorenyl, 4H-quinazinyl, isoquinolyl, quinolinyl, phthalazinyl, Naphthyridinyl, quinoxalinyl, quinazolinyl, Cinnolinyl, pteridinyl, 4aH-carbazolyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, Perimidinyl, phenolinyl, phenazinyl, phenarsazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl ), phenoxazine, different Isochromanyl, benzochromanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazolinyl, piperidinyl, piperazinyl, porphyrin Base, isoindolyl, Quinuclidinyl, morpholinyl and thioxantholyl.

Specific examples of the alkylthiocarbonyl group which may have a substituent include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, a octylthiocarbonyl group, a sulfonylthiocarbonyl group, an octadecylthiocarbonyl group, and Trifluoromethylthiocarbonyl.

Specific examples of the arylthiocarbonyl group which may have a substituent include 1-naphthylthiocarbonyl, 2-naphthylthiocarbonyl, 4-methylnonylphenylthiocarbonyl, 4-phenylmercaptophenylthiocarbonyl, 4-di Methylaminophenylthiocarbonyl, 4-diethylaminophenylthiocarbonyl, 2-chlorophenylthiocarbonyl, 2-methylphenylthiocarbonyl, 2-methoxyphenylthiocarbonyl, 2- Butoxyphenylthiocarbonyl, 3-chlorophenylthiocarbonyl, 3-trifluoromethylphenylthiocarbonyl, 3-cyanophenylthiocarbonyl, 3-nitrophenylthiocarbonyl, 4-fluorophenylsulfide Carbonyl, 4-cyanophenylthiocarbonyl And 4-methoxyphenylthiocarbonyl.

The monovalent substituent represented by the above B represents an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group. Further, these groups may have one or more substituents. The substituents described above can be exemplified as the substituents described above. Further, the substituents described above may be further substituted with other substituents.

Among them, the structure shown below is particularly preferable.

In the following structures, Y, X and n are the same as Y, X and n in the following formula (2), and preferred examples are also the same.

Examples of the divalent organic group represented by the above A include an alkylene group having 1 to 12 carbon atoms, a cyclohexylene group, and an alkynylene group. Further, these groups may have one or more substituents. The substituents described above can be exemplified as the substituents described above. Further, the substituents described above may be further substituted with other substituents.

Among them, in terms of improving sensitivity and suppressing coloring caused by heating over time, A is preferably an unsubstituted alkylene group, an alkyl group (for example, methyl group, ethyl group, tert-butyl group, and twelve groups). Alkyl) substituted alkylene, alkylene substituted by alkenyl (eg, vinyl, allyl), aryl (eg phenyl, p-tolyl, xylyl, cumenyl, naphthyl, Anthracenyl, phenanthryl, styryl) substituted alkylene.

The aryl group represented by the above Ar is preferably an aryl group having 6 to 30 carbon atoms, and It may also have a substituent. The substituent may be the same as the substituent introduced in the substituted aryl group exemplified above as a specific example of the aryl group which may have a substituent.

Among them, a substituted or unsubstituted phenyl group is preferred in terms of improving sensitivity and suppressing coloration caused by heating over time.

In the formula (1), in terms of sensitivity, the structure of "SAr" formed by the above Ar and the adjacent S is preferably the structure shown below. Further, Me represents a methyl group, and Et represents an ethyl group.

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

(In the 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 is an integer of 0 to 5)

R, A and Ar in the formula (2) have the same meanings as R, A and Ar in the above formula (1), and preferred examples are also the same.

The monovalent substituent represented by the above X may, for example, be an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a decyloxy group, a decyl group, an alkoxycarbonyl group, an amine group, a heterocyclic group or a halogen atom. Further, these groups may have one or more substituents. The substituents described above can be exemplified as the substituents described above. Further, the substituents described above may be further substituted with other substituents.

Among these, X is preferably an alkyl group in terms of improving solvent solubility and absorption efficiency in a long wavelength range.

Further, n in the formula (2) represents an integer of 0 to 5, preferably an integer of 0 to 2.

The divalent organic group represented by the above Y may be exemplified by the structure shown below. Further, among the groups shown below, * represents a bonding position of a carbon atom adjacent to Y in the above formula (2).

Among them, from the viewpoint of high sensitivity, the structure shown below is preferable.

Further, the ruthenium compound is also preferably a compound represented by the following formula (3).

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

Hereinafter, specific examples (PIox-1) to specific examples (PIox-13) of the ruthenium compound which can be preferably used are shown below, but the present invention is not limited to these compounds.

The ruthenium compound preferably has a maximum absorption wavelength in a wavelength range of 350 nm to 500 nm, more preferably an absorption wavelength in a wavelength range of 360 nm to 480 nm, and particularly preferably a high absorbance at 365 nm and 455 nm.

From the viewpoint of sensitivity, the molar absorption coefficient of the cerium compound at 365 nm or 405 nm is preferably 3,000 to 300,000, more preferably 5,000 to 300,000, and particularly preferably 10,000 to 200,000.

The molar absorption coefficient of the compound can be measured by a known method, and specifically, for example, it is preferably an ultraviolet-visible spectrophotometer (manufactured by Varian, Inc., a Carry-5 spectrophotometer). The ethyl acetate solvent was measured at a concentration of 0.01 g/L.

The photopolymerization initiator is more preferably a compound selected from the group consisting of an anthraquinone compound, an acetophenone-based compound, and a mercaptophosphine compound. More specifically, for example, an aminoacetophenone-based initiator as described in JP-A-10-291969, and a mercaptophosphine-based initiator as described in Japanese Patent No. 4,258,899, and The oxime-based initiator and the oxime-based initiator described above may also be a compound described in JP-A-2001-233842.

As the acetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all of BASF, Japan) can be used. Japan) manufactured by the company). Further, as the mercaptophosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (trade name: all manufactured by BASF Japan) can be used as a commercial product.

<Surfactant>

The composition of the present invention may also contain a surfactant. The surfactant may be used alone or in combination of two or more. The amount of the surfactant to be added is preferably from 0.001% by mass to 2.0% by mass, more preferably from 0.005% by mass to 1.0% by mass, even more preferably from 0.01% by mass to 0.1% by mass or less based on the total mass of the composition of the present invention. .

As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an anthrone-based surfactant can be used.

In particular, since the composition of the present invention contains a fluorine-based surfactant, the solution characteristics (especially fluidity) at the time of preparation of the coating liquid are further improved, so that the uniformity of the coating thickness or the liquid-saving property can be further improved.

In other words, when the film formation is carried out using a coating liquid using a composition containing a fluorine-based surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the surface to be coated is wetted. The properties are improved, and the coatability to the coated surface is improved. Therefore, even when a film having a thickness of a few micrometers (μm) is formed in a small amount of a solution, it is possible to more preferably form a film having a uniform thickness having a small thickness unevenness, which is effective in this respect.

The fluorine content in the fluorine-based surfactant is preferably from 3% by mass to 40% by mass, more preferably from 5% by mass to 30% by mass, even more preferably from 7% by mass to 25% by mass. The fluorine-based surfactant having a fluorine content in this range is effective in the uniformity of the thickness of the coating film or the liquid-saving property, and the solubility in the near-infrared absorbing composition is also good.

Examples of the fluorine-based surfactant include Megafac F171. Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Meijia Method (Megafac) F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Meijiafa (Megafac) F780, Megafac F781 (above is made by Di Aisheng (DIC)), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above) Made for Sumitomo 3M (shares), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, sand Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon ) KH-40 (above is manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA).

Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates (for example, propoxylated glycerol, ethoxylate). Glycerin, etc.), polyoxyethylene ethyl lauryl ether, polyoxyethylene ethyl stearyl ether, polyoxyethylene ethyl alkenyl ether, polyoxyethyl octyl phenyl ether, polyoxyethylene Phenylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, manufactured by BASF), Pronk (Pluronic) L31, Pro Pluronic L61, Pluronic L62, Pluronic 10R5, Pluronic 17R2, Pluronic 25R2, Tetronic 304, Tetronic 701, Tetronic 704, Tetronic 901, Tetronic 904, Tetronic 150R1, Solsperse 20000 (Lubrizol Japan) ) Manufacturing) and so on.

Specific examples of the cationic surfactant include a phthalocyanine derivative (trade name: EFKA-745, manufactured by Morishita Industries Co., Ltd.), an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (methyl) Acrylic (co)polymer Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (Yu Shang (share) manufacturing) and so on.

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

Examples of the anthrone-based surfactants include Toray Silicone DC3PA manufactured by Toray-Dow Corning Co., Ltd., Toray Silicone SH7PA, and East Toray Silicone DC11PA", "Toray Silicone SH21PA", "Toray Silicone SH28PA", "Toray Silicone SH29PA", "Dong Lizhen" Toray Silicone SH30PA, Toray Silicone SH8400, Momentive Performance Materials, "TSF-4440", "TSF-4300", "TSF-4445", " TSF-4460", "TSF-4452", "KP341", "KF6001", "KF6002" manufactured by Shin-Etsu Chemical Co., Ltd., and "BYK307", "BYK323", "BYK330" manufactured by BYK Chemie.

<Other ingredients>

In the near-infrared absorbing composition of the present invention, in addition to the above-mentioned essential components or the above-described preferred additives, other components may be appropriately selected depending on the purpose as long as the effects of the present invention are not impaired.

Examples of other components which can be used in combination include a dispersant, a sensitizer, a crosslinking agent, a curing accelerator, a filler, a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer, and the like, and may be used in combination with the surface of the substrate. Adhesion promoter and other auxiliary agents (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc.).

By appropriately containing these components, properties such as stability of the target near-infrared absorption filter and film physical properties can be adjusted.

For the above-mentioned components, for example, paragraphs 0183 to 0228 of JP-A-2012-003225, paragraph number 0101 to paragraph number 0102 of JP-A-2008-250074, and JP-A-2008-250074 The description of paragraph number 0103 to paragraph number 0104, paragraph number 0107 to paragraph number 0109 of Japanese Patent Laid-Open No. 2008-250074, and the like is incorporated herein by reference.

The near-infrared absorbing composition of the present invention can be made into a liquid form, so that, for example, a near-infrared can be easily manufactured by a simple step of forming a film by spin coating. The line cut filter can improve the insufficient manufacturing suitability of the above-described conventional near-infrared cut filter.

The use of the near-infrared ray absorbing composition of the present invention is not particularly limited, and examples thereof include a near-infrared cut filter for receiving light on the solid-state image sensor substrate (for example, a near-infrared cut filter for a wafer level lens). The near-infrared cut filter or the like on the back side of the solid-state image sensor substrate (the side opposite to the light-receiving side) is preferably a light-shielding film on the light-receiving side of the solid-state image sensor substrate. In particular, in the present invention, a coating film can be formed on an image sensor for a solid-state image sensor, and it is preferably used.

Further, the viscosity of the near-infrared absorbing composition of the present invention is preferably 1 mPa when the near-infrared cut-off layer is formed by coating. Above s, 3000mPa. Within the range of s below, more preferably 10mPa. Above s, 2000mPa. s the following range, and then preferably 100mPa. Above s, 1500mPa. s the following range.

When the near-infrared ray absorbing composition of the present invention is used for a near-infrared cut filter on the light-receiving side of a solid-state image sensor substrate, and a near-infrared cut-off layer is formed by coating, thick film formability and uniform coating property are obtained. From the point of view, the viscosity is preferably at 10 mPa. Above s, 3000mPa. Within the range of s below, more preferably 500mPa. Above s, 1500mPa. The range below s, the best is 700mPa. Above s, 1400mPa. s the following range.

The present invention also relates to a near-infrared cut filter which is obtained by using the near-infrared absorbing composition of the present invention described above. Such a near-infrared cut filter is formed by the near-infrared absorbing composition of the present invention, so it is a near-infrared region A near-infrared cut filter having a high light-shielding property (near-infrared shielding property), high light transmittance (visible light transmittance) in a visible light region, and excellent weather resistance such as light resistance and moisture resistance. Particularly in the present invention, it is advantageous as a near-infrared cut filter having a wavelength range of 700 nm to 2500 nm.

Furthermore, the present invention also relates to a method for fabricating a near-infrared cut filter, comprising the steps of: applying to a light-receiving side of a solid-state imaging device substrate (preferably coating or printing, and preferably spin coating or meshing) Printing) A near-infrared absorbing composition of the present invention, whereby a film is formed.

When a near-infrared cut filter is formed, a film is first formed by the near-infrared absorbing composition of the present invention described above. The film is not particularly limited as long as it is a film formed by containing the above-mentioned near-infrared absorbing composition, and the film thickness, the laminated structure and the like can be appropriately selected depending on the purpose.

The method for forming the film includes a method in which a near-infrared absorbing composition of the present invention is directly applied (preferably applied) to a support (the solid component in the composition is dissolved, emulsified or dispersed in the solvent). The resulting coating liquid) was dried to thereby form the above film.

The support may be a solid-state imaging device substrate, or may be another substrate (for example, a glass substrate 30 to be described later) provided on the light-receiving side of the solid-state imaging device substrate, or may be a layer such as a planarization layer provided on the light-receiving side of the solid-state imaging device substrate. .

The method of applying the near-infrared absorbing composition (coating liquid) to the support can be carried out, for example, by using a spin coater, a slit spin coater or the like.

In addition, the drying conditions of the coating film are also based on the type of each component and solvent. It varies depending on the ratio, etc., and is usually dried at a temperature of 60 ° C to 150 ° C for about 30 seconds to 15 minutes.

The thickness of the film is not particularly limited and may be appropriately selected depending on the purpose, and is, for example, preferably 1 μm to 100 μm, more preferably 1 μm to 50 μm, still more preferably 1.0 μm to 4.0 μm.

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

The other steps described above are not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include a surface treatment step of the substrate, a pre-heating step (pre-baking step), a hardening treatment step, a post-heating step (post-baking step), and the like. .

<Preheating step, post heating step>

The heating temperature in the pre-heating step and the post-heating step is usually from 80 ° C to 200 ° C, preferably from 90 ° C to 150 ° C.

The heating time in the pre-heating step and the post-heating step is usually from 30 seconds to 240 seconds, preferably from 60 seconds to 180 seconds.

<hardening treatment step>

The hardening treatment step is a step of hardening the formed film as needed, and by performing this treatment, the mechanical strength of the near-infrared cut filter is improved.

The hardening treatment step is not particularly limited and may be appropriately selected depending on the purpose. For example, a total exposure treatment, a total heat treatment, or the like can be preferably exemplified. Here, the term "exposure" in the present invention is used as follows: not only various wavelengths are included The light also includes radiation such as electron beams and X-rays.

The exposure is preferably performed by irradiation of radiation, and ultraviolet rays or visible light such as electron beams, KrF, ArF, g-rays, h-rays, and i-rays can be preferably used for radiation to be used for exposure. Preferably, KrF, g-ray, h-ray, and i-ray are preferred.

Examples of the exposure method include stepwise exposure or exposure using a high pressure mercury lamp.

The exposure amount is preferably ⁵ mJ/cm ² to 3000 mJ/cm ² , more preferably 10 mJ/cm ² to 2000 mJ/cm ² , and most preferably 50 mJ/cm ² to 1000 mJ/cm ² .

The method of the full exposure treatment includes, for example, a method of exposing the entire surface of the formed film. When the near-infrared absorbing composition contains a polymerizable compound, the curing of the polymer component in the film formed by the above composition is promoted by total exposure, and the curing of the film is further progressed, and mechanical strength and durability are obtained. Improvement.

The apparatus for performing the above full exposure is not particularly limited, and may be appropriately selected depending on the purpose. For example, an ultraviolet (UV) exposure machine such as an ultrahigh pressure mercury lamp can be preferably used.

Further, the method of the overall heat treatment may be a method of heating the entire surface of the formed film. The film strength of the pattern can be increased by full heating.

The heating temperature for the overall heating is preferably from 120 ° C to 250 ° C, more preferably from 120 ° C to 250 ° C. 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 can be prevented. The decomposition occurs and the film becomes weak and brittle.

The heating time for the overall heating is preferably from 3 minutes to 180 minutes, more preferably from 5 minutes to 120 minutes.

The apparatus for performing overall heating is not particularly limited, and may be appropriately selected according to the purpose from known apparatuses, and examples thereof include a dry oven, a hot plate, and an infrared ray (IR) heater.

Further, the present invention relates to an image pickup module including a solid-state image sensor substrate and a near-infrared cut filter disposed on a light receiving side of the solid-state image sensor substrate, and the near-infrared cut filter is a near-invention of the present invention Infrared cut filter.

Hereinafter, an imaging module according to an embodiment of the present invention will be described with reference to Figs. 1 and 2, but the present invention is not limited to the following specific examples.

In addition, in FIG. 1 and FIG. 2, the common part is attached with the common code.

In addition, in the description, "upper", "upper" and "upper side" refer to the side away from the substrate 10, and "lower", "lower" and "lower side" refer to the side closer to the substrate 10 .

FIG. 1 is a schematic cross-sectional view showing a configuration of an image pickup module including a solid-state image sensor.

The camera module 200 shown in FIG. 1 is connected to a circuit board 70 as a package substrate via a solder ball 60 as a connection member.

Specifically, the image pickup module 200 is configured to include a solid-state image sensor substrate 100 including an image sensor element portion on a first main surface of the ruthenium substrate, and is provided on A planarization layer 46 (not shown in FIG. 1) on the first main surface side (light receiving side) of the solid-state imaging device substrate 100, a near-infrared cut filter 42 provided on the planarization layer 46, and a near-infrared cut filter The glass substrate 30 (light-transmitting substrate) above the device 42 , the lens holder 50 disposed above the glass substrate 30 and having the imaging lens 40 in the internal space, and the periphery surrounding the solid-state imaging device substrate 100 and the glass substrate 30 The configuration is provided with a light-shielding and electromagnetic shield (shield) 44. Each member is bonded by an adhesive 20 (not shown in FIG. 1) and an adhesive 45.

Further, the present invention relates to a method of manufacturing an image pickup module, which is a method of manufacturing an image pickup module including a solid-state image sensor substrate and a near-infrared cut filter disposed on a light receiving side of the solid-state image sensor substrate, and the image pickup unit In the method of manufacturing a module, the near-infrared absorbing composition of the present invention is applied to the light-receiving side of the solid-state image sensor substrate to form a film.

Therefore, in the imaging module of the present embodiment, for example, the near-infrared absorbing composition of the present invention is applied onto the planarization layer 46, whereby a film is formed to form the near-infrared cut filter 42. The method of manufacturing a near-infrared cut filter by coating to form a film is as described above.

In the imaging 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, and then reaches the imaging element portion of the solid-state imaging device substrate 100.

Further, the camera module 200 is connected to the circuit board 70 via the solder ball 60 (connection material) on the second main surface side of the solid-state image sensor substrate 100.

FIG. 2 is a cross-sectional view showing the solid-state imaging element substrate 100 in FIG. 1 enlarged.

The solid-state imaging device substrate 100 is configured to include a germanium substrate 10 as a substrate, an image sensor 12, an interlayer insulating film 13, a matrix layer 14, a red color filter 15R, a green color filter 15G, and a blue color. The color filter 15B, the overcoat layer 16, the microlens 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.

Among them, the solder resist layer 24 can also be omitted.

First, the configuration of 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 portion is provided on the first main surface side of the substrate 10 as a base of the solid-state imaging device substrate 100, and the imaging element portion is formed by arranging a plurality of imaging elements 12 such as a CCD or a CMOS in two dimensions. Made.

An interlayer insulating film 13 is formed on the image pickup element 12 of the image pickup element portion, and a matrix layer 14 is formed on the interlayer insulating film 13. Further, a red color filter 15R, a green color filter 15G, and a blue color filter 15B are disposed on the substrate layer 14 so as to correspond to the image sensor 12 (hereinafter sometimes These are collectively referred to as "color filters").

A light shielding film (not shown) may be provided at a 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 portion. The light-shielding film can be produced, for example, using a known black color resist.

An overcoat layer 16 is formed on the color filter, and a microlens 17 is formed on the overcoat layer 16 so as to correspond to the image pickup element 12 (color filter).

Further, the above-described planarization layer 46 is provided on the microlens 17.

Further, a peripheral circuit (not shown) and an internal electrode 26 are provided around the imaging element portion on the first main surface side, and the internal electrode 26 is electrically connected to the imaging element 12 via a peripheral circuit.

Further, the element surface electrode 27 is formed on the internal electrode 26 via the interlayer insulating film 13. A contact plug (not shown) that electrically connects the electrodes is formed in the interlayer insulating film 13 between the internal electrode 26 and the element surface electrode 27. The element surface electrode 27 is used for voltage application, signal reading, and the like via the contact plug and the internal electrode 26.

A matrix layer 14 is formed on the element surface electrode 27. An overcoat layer 16 is formed on the substrate layer 14. The substrate layer 14 and the overcoat layer 16 formed on the element surface electrode 27 are opened to form a pad opening portion, 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, but may be provided between the substrate layer 14 and the color filter or between the color filter and the overcoat layer 16. A near-infrared cut filter 42 is provided on the planarization layer 46 instead of the near-infrared cut filter 42.

On the first main surface side of the solid-state imaging device substrate 100, an adhesive 20 is provided around the imaging element portion, and the solid-state imaging device substrate 100 and the glass substrate 30 are bonded via the adhesive 20 .

Further, the ruthenium substrate 10 has a through hole penetrating the ruthenium substrate 10, and a through electrode as 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 of 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.

The patterned metal electrode 23 is provided on the insulating film 22 so as to extend from the region on the second main surface of the substrate 10 to the inside of the through hole. The metal electrode 23 is an electrode for connecting the imaging element portion of the solid-state imaging element substrate 100 to the circuit substrate 70.

The through electrode is a portion of the metal electrode 23 formed inside the through hole. The through electrode penetrates a part of the germanium substrate 10 and the interlayer insulating film to reach the lower side of the internal electrode 26, and is electrically connected to the internal electrode 26.

Further, a solder resist layer 24 (protective insulating film) is provided on the second main surface side, and the solder resist layer 24 (protective insulating film) covers the second main surface on which the metal electrode 23 is formed, and has the metal electrode A portion of the opening portion of the portion 23 is exposed.

Then, a light shielding film 18 is provided on the second main surface side, and the light shielding film 18 covers the second main surface on which the solder resist layer 24 is formed, and has an opening portion in which a part of the metal electrode 23 is exposed.

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 portion. However, the light-shielding film 18 can be patterned so that the metal electrode 23 is entirely exposed (solder resist layer). The patterning of 24 is also the same).

Further, the solder resist layer 24 may be omitted, or 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 image sensor substrate 100 and the connection electrode (not shown) of the circuit board 70 are electrically connected via the solder ball 60. .

In the above, the configuration of the solid-state imaging device substrate 100 has been described. However, the method described in paragraphs 0033 to 0068 of Japanese Patent Laid-Open Publication No. 2009-158863, or Japanese Patent Laid-Open No. 2009-99591 The imaging element substrate 100 is formed by a known method such as the method described in paragraphs 0036 to 0065.

The interlayer insulating film 13 is formed, for example, by sputtering, chemical vapor deposition (CVD), or the like in the form of a SiO ₂ film or a SiN film.

The color filter is formed, for example, by photolithography using a known color resist.

The overcoat layer 16 and the underlayer 14 are formed, for example, by photolithography using a known resist for forming an organic interlayer film.

The microlens 17 is formed by, for example, photolithography using a styrene polymer or the like.

The solder resist layer 24 is preferably formed by photolithography using, for example, a known solder resist containing a phenol-based polymer, a polyimide-based polymer, or an amine-based polymer.

The solder ball 60 is, for example, Sn-Pb (eutectic), 95Pb-Sn (high-lead high-melting solder), Sn-Ag, Sn-Cu, Sn-Ag-Cu, etc. as lead-free (Pb) solder. To form. The solder ball 60 is formed, for example, in a spherical shape having a diameter of 100 μm to 1000 μm (preferably, a diameter of 150 μm to 700 μm).

The internal electrode 26 and the element surface electrode 27 are formed, for example, by a metal electrode such as Cu by chemical mechanical polishing (CMP) or photolithography.

The metal electrode 23 is formed of, for example, a metal electrode such as Cu, Au, Al, Ni, W, Pt, Mo, a Cu compound, a W compound, or a Mo compound by sputtering, photolithography, etching, and plating. The metal electrode 23 may have a single layer structure or a laminate structure including two or more layers. The film thickness of the metal electrode 23 is set to, for example, 0.1 μm to 20 μm (preferably 0.1 μm to 10 μm). The tantalum substrate 10 is not particularly limited, and a tantalum substrate which is thinned by cutting the back surface of the substrate can be used. The thickness of the substrate is not limited, and for example, a tantalum wafer having a thickness of 20 μm to 200 μm (preferably 30 μm to 150 μm) is used.

The through hole of the ruthenium substrate 10 is formed, for example, by photolithography and reactive ion etching (RIE).

Although an embodiment of the imaging module has been described above with reference to FIGS. 1 and 2, the above-described embodiment is not limited to the embodiment of FIGS. 1 and 2.

Example

The invention is more specifically illustrated by the following examples. The materials, the amounts used, the ratios, the processing contents, the processing order, and the like shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, as long as there is no special explanation, "parts" and "%" are Quality benchmark.

<Compound preparation method>

Copper benzoate (manufactured by Kanto Chemical Co., Ltd., 3.8 g) and 1 g of the phosphate compound described in the following table were added to the acetone solution. After stirring for 3 hours, hexane reprecipitation was carried out twice, whereby an oily compound was obtained.

<Measurement of λmax>

0.2 g of the complex was prepared by using 20 mL of THF to prepare a solution, and a light absorption coefficient of λ max and λ max was measured by measuring 400 nm to 1100 nm using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Co., Ltd.).

<Measurement of gram absorption coefficient (g/ml)>

The absorbance/concentration (g/mL) of λmax measured by the above method was taken as the gram extinction coefficient.

<O=Measurement of P-O angle>

The calculation was carried out based on the stable configuration obtained by the molecular mechanics calculation of MM2 (manufactured by Fujitsu, Scigress), thereby measuring the O=P-O angle.

<Measurement of O-P-O Angle>

The O-P-O angle was measured by calculation based on the stable configuration obtained by molecular mechanics calculation by MM2 (manufactured by Fujitsu, Scigress).

The O=P-O angle and the O-P-O angle of the phosphate compound used in the examples of the present application are shown below.

The samples in the above table were formulated at a ratio of 1:1 (about Moule ratio) in the case of using a mixture of two phosphate compounds.

It is apparent from the above table that the near-infrared absorbing agent of the present invention achieves a high gram absorption coefficient.

The following compounds were mixed to prepare a near-infrared absorbing composition.

The obtained near-infrared absorbing composition was subjected to the following evaluation.

[Evaluation method]

<Evaluation of Near Infrared Absorbing Composition>

(production of near-infrared cut filter)

Each of the prepared near-infrared absorbing compositions was spin-coated by a spin coating method (using MIKASA SPINCOATER 1H-D7; 340 rpm) manufactured by MIKASA Co., LTD. On the glass substrate, preheating (prebaking) was performed at 100 ° C for 120 seconds. Further, a part of the samples were subjected to total exposure at 2000 mJ/cm ² using an i-ray stepper. Thereafter, all the samples were heated at 180 ° C for 180 seconds using a hot plate to obtain a near-infrared cut filter.

(Near infrared shielding evaluation)

The near infrared ray cut as obtained above was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Co., Ltd.) The transmittance of the filter at a wavelength of 900 nm. The minimum value of the transmittance (%) in the near-infrared range of 1000 nm was used as an index of the shielding property. When the near-infrared transmittance is 5% or less with respect to the transmittance, it is practically excellent in near-infrared shielding properties.

(heat resistance evaluation)

The substrate obtained as described above was further subjected to heat treatment at 220 ° C for 3 minutes by a hot plate. Before the heat resistance test and the heat resistance test, the maximum absorbance of the near-infrared cut filter at a wavelength of 700 nm to 1400 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Co., Ltd.). Abs λ max) and the minimum absorbance (Abs λ min) at a wavelength of 400 nm to 700 nm, and the absorbance ratio expressed by "Abs λ max / Abs λ min " was obtained. The absorbance ratio change rate indicated by | (absorbance ratio before test - absorbance ratio after test) / absorbance before test × 100 | (%) was evaluated according to the following criteria.

A: Absorbance ratio change rate ≦2%

B: 2% < absorbance ratio change rate ≦ 4%

C: 4% < absorbance ratio change rate ≦ 7%

D: 7% < absorbance ratio change rate

(filming property evaluation)

The minimum value of the transmittance (%) in the near-infrared range of the wavelength of 1000 nm of the near-infrared cut filter obtained as described above was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Co., Ltd.). A near-infrared cut filter film was formed so that the near-infrared transmittance was 5% or less, and the surface of the film was visually observed. The results were classified and determined as follows.

A: Cracks and unevenness are not confirmed at all in the surface, and it is practical.

B: Cracks and unevenness are confirmed on the surface, and it is not practical.

In the same manner as the composition 1, the composition 2 to the composition 29 as shown in the following Table was prepared and evaluated.

The evaluation of the near-infrared ray shielding properties of the obtained near-infrared absorbing composition showed that the near-infrared transmittance was 5% or less.

Further, in the preparation of the near-infrared absorbing composition 1 to the near-infrared absorbing composition 23, even when the polymerizable compound is changed to JER157S65 (epoxy resin, manufactured by Nippon Epoxy Co., Ltd.), Good results can be obtained in the same way.

Further, even when the solvent was changed to propylene glycol monomethyl ether (PGME) or cyclohexanone, good results were obtained in the same manner.

30‧‧‧ glass substrate

40‧‧‧ camera lens

42‧‧‧Near-infrared cut-off filter

44‧‧‧Shading and electromagnetic shielding

45‧‧‧Adhesive

50‧‧‧ lens holder

60‧‧‧ solder balls

70‧‧‧ circuit board

100‧‧‧Solid imaging element substrate

200‧‧‧ camera module

Hν‧‧‧ incident light

Claims (15)

A near-infrared ray absorbing agent containing a copper phosphate complex which is formed by reacting a phosphodiester compound represented by the following formula with a copper salt; (In the above formula, R is an organic group; and O = PO angle is in the range of 104 to 120 degrees). The near-infrared ray absorbing agent according to claim 1, wherein the phosphodiester compound has an O=P-O angle of 110 degrees or less. The near infrared ray absorbing agent according to claim 1 or 2, wherein the phosphodiester compound has an O-P-O angle of from 104 to 109.5 degrees. The near infrared ray absorbing agent according to claim 1 or 2, wherein the chrome absorption coefficient of the copper phosphate complex is 0.03 g/ml or more, wherein the gram absorption coefficient is absorbance/concentration (so-called concentration) , means the weight (g) per 1 mL). The near-infrared ray absorbing agent according to claim 1 or 2, wherein the copper phosphate complex has a maximum absorption wavelength of 790 nm to 850 nm. The near-infrared ray absorbing agent according to claim 1 or 2, wherein the phosphodiester compound has an OPO angle of from 104 to 109.5 degrees, and the gram absorbance coefficient of the copper phosphate complex is 0.03 g/ Ml or more, wherein the gram absorption coefficient is absorbance/concentration (so-called concentration, which means every 1 mL Weight (g)). The near infrared ray absorbing agent according to claim 1 or 2, wherein the phosphodiester compound has an OPO angle of from 104 to 109.5 degrees, and the maximum absorption wavelength of the copper phosphate complex is from 790 nm to 850 nm. . The near infrared ray absorbing agent according to claim 1 or 2, wherein the phosphodiester compound has an OPO angle of from 104 to 109.5 degrees, and the maximum absorption wavelength of the copper phosphate complex is from 790 nm to 850 nm. The gram absorbance coefficient of the copper phosphate complex is 0.03 g/ml or more, and the gram absorbance is absorbance/concentration (so-called concentration means weight per gram (g)). A near-infrared absorbing composition containing a near-infrared ray absorbing agent, a polymerizable compound, and a solvent according to any one of claims 1 to 8, and the phosphoric acid in the near-infrared absorbing composition The concentration of the ester copper complex is from 10% by mass to 80% by mass. The near-infrared absorbing composition according to claim 9, wherein the compounding amount of the copper phosphate complex is 50% by mass to 99% by mass based on the total solid content of the near-infrared absorbing composition. The near-infrared absorbing composition according to claim 9, which is used for forming a coating film on an image sensor for a solid-state imaging device. A near-infrared ray-eliminating filter which uses the near-infrared ray absorbing agent according to any one of claims 1 to 8 or the near-infrared absorbing composition as described in claim 9 of the patent application. Production. An image pickup module comprising a solid-state image sensor substrate and a near-infrared cut filter according to claim 12, which is disposed on a light receiving side of the solid-state image sensor substrate. A method of manufacturing an image pickup module, comprising: a solid-state image sensor substrate; and a method of manufacturing an image pickup module disposed on a light-receiving side near-infrared cut filter of the solid-state image sensor substrate, and the method of manufacturing the image pickup module includes In the step of coating the near-infrared absorbing composition described in claim 9 on the light-receiving side of the solid-state image sensor substrate, a film is formed. The method of manufacturing a camera module according to claim 14, comprising: curing the film formed by applying the near-infrared absorbing composition by light irradiation.